Spoiler coil coating cooling drum for high flux lithium metal deposition

Abstract

The invention relates to vapor deposition systems and methods. In one embodiment, a drum for vapor deposition is provided. The drum includes a housing having a gas slit and a cooling drum. The cooling drum includes an outer region, an inner region, a first fluid channel defined in part by the outer region and the inner region, and a first inlet. The first fluid passage forms a helical passage around a central axis of the cooling drum. The first inlet is in fluid communication with the first outlet through the first fluid channel.

Description

Technical Field

[0001]

[0014] Embodiments described herein generally relate to metal electrodes, particularly lithium-containing anodes, high performance electrochemical components, such as primary and secondary electrochemical components, including such lithium-containing electrodes, and methods of making such electrodes. Background Art

[0002] Lithium (Li)-ion batteries have played a vital role in the development of modern mobile devices, microelectronics, and electric vehicles. A typical Li-ion battery consists of a positive electrode (cathode), a negative electrode (anode), an electrolyte to conduct ions, a porous separator (electrical insulator) to maintain a physical separation between the two electrodes, and packaging.

[0003] Methods for depositing lithium on substrates such as large flexible substrates can be temperature sensitive and lead to the formation of wrinkles and other defects. The substrate can be guided and supported on a rotatable coating drum having a curved drum surface. As the substrate moves over the curved drum surface of the rotatable drum, vapor can be deposited on the substrate as the substrate passes over the evaporation source or sources. The drum can be used to maintain a high heat transfer rate and control the temperature of the substrate by utilizing high pressure cooling and applying pressure to the back side of the substrate to maintain a uniform gap height between the substrate and the curved drum surface. For wide film substrates, machine direction wrinkles caused by particles, film stress or misalignment can be corrected using low web tension.

[0004] Therefore, apparatus and methods are needed to maintain low pressure and enhance substrate cooling to increase processing throughput. Summary of the Invention

[0005] The present disclosure relates to vapor deposition systems and methods. In one embodiment, a drum for vapor deposition is provided. The drum includes a housing having a gas slit and a cooling drum. The cooling drum includes an outer region, an inner region, a first fluid channel partially defined by the outer region and the inner region, and a first inlet. The first fluid channel forms a spiral channel around a central axis of the cooling drum. The first inlet is in fluid communication with a first outlet via the first fluid channel.

[0006] In one embodiment, a roll-to-roll deposition system is provided. The roll-to-roll deposition system includes an evaporation unit, a plurality of tension rollers, and a drum. The drum is disposed between the plurality of tension rollers and the evaporator unit. The drum includes a housing having a gas slit and a cooling drum. The cooling drum includes an outer region, an inner region, a first fluid channel, and a first inlet. The first fluid channel is partially defined by the outer region and the inner region. The first fluid channel forms a spiral channel around a central axis of the cooling drum. The first inlet is fluidically connected to a first outlet via the first fluid channel.

[0007] In one embodiment, a method for applying an anode material to a substrate is provided. The method includes supplying a coolant to a drum. The drum includes a housing and a cooling drum disposed radially inwardly within the housing. The cooling drum has a first fluid channel. The first fluid channel is defined in part by an outer region and an inner region of the cooling drum, the first fluid channel forming a spiral channel around a central axis of the cooling drum. The method also includes flowing the coolant through the first fluid channel, flowing a gas through a cavity between the housing and the cooling drum, deploying the substrate onto the housing, and evaporating the anode material onto the substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] In order that the above-mentioned features of the present disclosure may be understood in detail, reference will now be made to a more particular description of the present disclosure, some of which are illustrated in the accompanying drawings. However, it must be noted that the drawings illustrate only exemplary embodiments and are therefore not to be considered limiting of its scope, and that other equally effective embodiments may be encompassed.

[0009] Figure 1 A cross-sectional view of one embodiment of an energy storage element including an anode electrode structure is schematically illustrated according to certain embodiments described in the present disclosure.

[0010] Figure 2 A cross-sectional view of one embodiment of a double-sided anode electrode structure is schematically illustrated according to certain embodiments described in the present disclosure.

[0011] Figure 3 A cross-sectional view of an evaporation source is schematically shown according to certain embodiments described in the present disclosure for depositing an evaporated material on a substrate.

[0012] Figure 4A A schematic diagram of a roll-to-roll unit including rollers is shown according to certain embodiments described in the present disclosure.

[0013] Figure 4B The internal geometry of the channel area of ​​the drum is schematically illustrated according to certain embodiments described in this disclosure.

[0014] Figure 4C is a schematic cross-sectional view of a drum according to certain embodiments described in the present disclosure.

[0015] Figure 5A A view of the interior of a drum fluid channel is schematically illustrated according to certain embodiments described in this disclosure.

[0016] Figure 5B According to certain embodiments described in this disclosure, Figure 5A A view of the interior of the fluid channel.

[0017] Figure 6 A flow chart schematically illustrates a method of cooling a substrate when using a roll-to-roll deposition system including a roller, according to certain embodiments described herein.

[0018] To facilitate understanding, like reference numerals in the figures have been used to designate common, like elements. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation. DETAILED DESCRIPTION

[0019] Vapor deposition systems used to coat a web of substrates guided on a rotatable coating drum are referred to herein as roll-to-roll (R2R) deposition systems. As described herein, flexible substrates can include many other materials, such as films, foils, webs, plastic strips, metals, paper, or other materials. Generally, the terms "web," "foil," "strip," and "substrate" are used interchangeably.

[0020] Energy storage elements, such as lithium-ion batteries, typically include a positive electrode (e.g., a cathode) and a negative electrode (e.g., an anode), which are separated by a polymer separator with a liquid electrolyte. Solid-state batteries also typically include a positive electrode and a negative electrode, but use an ion-conducting material instead of a polymer separator and a liquid electrolyte. Lithium is deposited on a substrate by evaporating molten lithium and condensing lithium vapor onto the substrate, such as a graphite-coated copper foil, copper foil, or a copper-coated polymer film. When lithium is deposited on the front side of the substrate, the substrate is maintained at a certain temperature below a certain level. Maintaining the temperature can include cooling the back side of the substrate by venting a gas between the surface of a roller supporting the substrate and the substrate. The deposition rate of lithium on the substrate is limited by the cooling rate of the back side of the substrate. The cooling gas is selected so as not to react with lithium. In certain embodiments, the cooling gas can be or include argon, helium, or a combination thereof.

[0021] In addition to supplying cooling gas to the back side of the substrate, a uniform gap distance between the substrate and the drum surface is typically maintained. Traditional solutions for retaining the substrate include high tension (e.g., web tension exceeding 100 Newtons per meter) and mechanical solutions, such as placing retention rollers around the drum to hold the substrate on the drum and prevent it from bulging off the drum when gas is applied and the substrate thermally expands. These solutions can cause web edge damage and coating detachment. It has been discovered that using Coulomb electrostatic adsorption can retain the substrate on the drum and maintain a uniform gap between the substrate and the drum surface.

[0022] In some embodiments, the substrate is a flexible substrate that is supported on the curved drum surface of the rotatable drum during the deposition process. Specifically, the substrate can pass through a plurality of nozzles to deposit the material on the substrate on the curved drum surface of the rotatable drum.

[0023] The substrate can be a flexible substrate, such as a flexible polymer material or a flexible metal foil, more particularly a copper foil or a copper-containing foil, such as a foil coated on one or both sides with copper. The thickness of the substrate can be 50 μm or less, particularly 20 μm or less, for example, about 8 μm. In certain embodiments, the substrate can be a thin copper foil (e.g., 4 μm thick or 6 μm thick) having a thickness in the range of less than 20 μm.

[0024] According to certain embodiments, which can be combined with other embodiments described herein, a battery anode is fabricated, and the flexible substrate comprises or consists of copper or a copper alloy. According to certain embodiments, the coil can also comprise graphite, silicon, silicon oxide, or any combination thereof. For example, lithium can pre-lithiate the layer comprising graphite, silicon, and / or silicon oxide.

[0025] Evaporative deposition of metals (e.g., lithium) onto flexible substrates (e.g., copper substrates) can be used to fabricate batteries, such as lithium batteries. For example, a lithium layer can be deposited onto a thin, flexible substrate to create the battery's anode. After assembling the anode and cathode layer stacks, optionally with the addition of an electrolyte and / or separator, the resulting layer arrangement can be rolled or otherwise stacked to produce a lithium battery.

[0026] Figure 1 A cross-sectional view of one embodiment of an energy storage element 100 is schematically shown, the device comprising an anode electrode structure 110 formed according to an embodiment of the present disclosure. The anode electrode structure 110 includes an anode membrane 170 having one or more ceramic protective films. The energy storage element 100 can be a solid-state energy storage element or a lithium-ion based energy storage element. Although the energy storage element 100 is shown as a planar structure, it can also be formed into a cylinder by stacking rolled layers; in addition, other battery configurations (such as prismatic batteries, button cells, or stacked electrode batteries) can also be formed. The energy storage element 100 includes an anode electrode structure 110 and a cathode electrode structure 120, optionally with an electrolyte or polymer separator 130 interposed therebetween. The cathode electrode structure 120 includes a cathode current collector 140 and a cathode membrane 150.

[0027] The one or more protective films 180 include one or more ceramic materials, which may be oxides, nitrides, or fluorides or carbonates that are soluble in the electrolyte. In one embodiment, the one or more ceramic protective films 180 include, for example, aluminum oxide (Al2O3), lithium fluoride (LiF), lithium carbonate (Li2CO3), aluminum oxynitride, aluminum nitride (AlN, aluminum deposited in a nitrogen environment), aluminum hydroxide ((AlO(OH))) (such as pegmatite ((α-AlO(OH))), bomaite (γ-AlO(OH)) or akedalite (5Al2O3·H2O)), calcium carbonate (CaCO3), titanium dioxide (TiO2), SiS2, SiPO4, silicon oxide (SiO2), zirconium oxide (ZrO2), hafnium oxide (HfO2), MgO, TiO2, Ta2O5, Nb2O5, LiAlO2, BaTiO3, boron nitride (BN), ion-conducting garnet, ion-conducting perovskite, ion-conducting antiperovskite, porous glass-ceramics, etc. or combinations thereof. In certain embodiments, the one or more ceramic protective films 180 are deposited using the evaporation technique described herein.

[0028] In certain embodiments, each layer of the one or more protective films 180 is a coating or discrete film having a thickness ranging from about 1 nm to about 3,000 nm (e.g., ranging from about 10 nm to about 600 nm; ranging from about 50 nm to about 100 nm; ranging from about 50 nm to about 200 nm; ranging from about 100 nm to about 150 nm).

[0029] The cathode electrode structure 120 includes a cathode current collector 140, and a cathode film 150 is formed on the cathode current collector 140. It should be understood that the cathode electrode structure 120 may include other elements or films.

[0030] The current collectors 140 and 160 on the cathode film 150 and the anode film 170 can be the same or different electron conductors. In certain embodiments, at least one of the current collectors 140 and 160 is a flexible substrate. The flexible substrate may be a CPP film (i.e., cast polypropylene film), an OPP film (i.e., oriented polypropylene film), or a PET film (i.e., polyethylene terephthalate film). Alternatively, the flexible substrate may be pre-coated paper, a polypropylene (PP) film, a PEN film, a polylactic acid (PLA) film, or a PVC film. Examples of metals that the current collectors 140 and 160 may comprise include aluminum (Al), copper (Cu), zinc (Zn), nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr), stainless steel, interlayer materials, alloys thereof, and combinations thereof. In one embodiment, at least one of the current collectors 140 and 160 is porous. In one embodiment, at least one of the current collectors 140 and 160 comprises a polymer substrate (e.g., a polyethylene terephthalate ("PET") surface coated with a metal material). In one embodiment, the anode current collector 160 is a polymer substrate coated with copper (e.g., a PET film). In another embodiment, the anode current collector 160 is a multi-metal layer located on a polymer substrate. The multi-metal layer can be a combination of copper, chromium, nickel, alloys of these metals, or any combination thereof. In one embodiment, the anode current collector 160 is a multi-layer structure comprising a copper-nickel cladding material. In one embodiment, the multi-layer structure includes a layer of nickel or chromium, a second layer of copper formed on the first layer, and a third layer of nickel, chromium, or both formed on the second layer. In one embodiment, the anode current collector 160 is nickel-plated copper. In one embodiment, the anode current collector 160 is graphite-plated copper. In addition, the current collector can be of any shape (e.g., metal foil, sheet, or plate), shape, and micro / macro structure.

[0031] In one embodiment, the cathode current collector 140 is aluminum. In another embodiment, the cathode current collector 140 can be or include aluminum deposited on a polymer substrate (e.g., a PET film). The thickness of the cathode current collector 140 is less than 50 μm, more specifically, 5 μm, or even more specifically, 2 μm. The thickness of the cathode current collector 140 ranges from about 0.5 μm to about 20 μm (e.g., from about 1 μm to about 10 μm; from about 2 μm to about 8 μm; or from about 5 μm to about 10 μm). In one embodiment, the anode current collector 160 is copper. In one embodiment, the anode current collector 160 is stainless steel. In one embodiment, the thickness of the anode current collector 160 is less than 50 μm, more specifically, less than or about 5 μm, or even more specifically less than or about 2 μm. In one embodiment, the anode current collector 160 has a thickness ranging from about 0.5 μm to about 20 μm (eg, from about 1 μm to about 10 μm; from about 2 μm to about 8 μm; from about 6 μm to about 12 μm; or from about 5 μm to about 10 μm).

[0032] The cathode film 150 or cathode can be any material that is compatible with the anode and can include an intercalation compound, an insertion compound, or an electrochemically active polymer.

[0033] The anode electrode structure 110 includes an anode current collector 160 and an anode film 170 formed on the anode current collector 160. The anode electrode structure 110 includes one or more ceramic protective films 180.

[0034] In certain embodiments, the anode film 170 is composed of lithium metal, lithium metal foil, or lithium alloy foil (e.g., lithium aluminum alloy or lithium tin alloy), or is a mixture of lithium metal and / or lithium alloy with carbon (e.g., coke, graphite), nickel, copper, tin, indium, silicon, their oxides, or any combination thereof. The anode film 170 can be or include one or more lithium-containing intercalation compounds or lithium-containing insertion compounds. In certain embodiments, the anode film is a lithium metal film. In certain embodiments, if the anode film 170 can be or include lithium metal, the lithium metal can be deposited using the methods described herein.

[0035] In certain embodiments, the anode film 170 may be or include graphite, silicon, or any combination thereof. The anode film 170 may be or include one or more carbonaceous materials, such as natural graphite or artificial graphite, partially graphitized or amorphous carbon, petroleum, coke, needle coke, and various intermediate phases, silicon-containing graphite, silicon, nickel, copper, tin, indium, aluminum, silicon, oxides thereof, combinations thereof, or mixtures of lithium metal and / or lithium alloys with materials such as carbon (e.g., coke or graphite), nickel, copper, tin, indium, aluminum, silicon, oxides thereof, or combinations thereof. In one example, the anode film 170 may be or include silicon-graphite. In another example, the anode film 170 may be or include graphite.

[0036] In certain embodiments, when the anode film 170 may be or include graphite, silicon, or silicon-graphite, a layer of lithium metal is formed on the surface of the anode film 170. The thickness of the lithium metal layer is between about 20 μm and about 50 μm. The lithium layer may be a pre-lithiation layer.

[0037] In one embodiment, the thickness of the anode film 170 is between about 10 μm and about 200 μm (e.g., between about 1 μm and about 100 μm; between about 10 μm and about 30 μm; between about 20 μm and about 30 μm; between about 1 μm and about 20 μm; or between about 50 μm and about 100 μm).

[0038] In certain embodiments, polymer membrane 130 is a membrane, which is a porous polymer ion conductive polymer substrate. In one embodiment, the porous polymer substrate is a multilayer polymer substrate. In certain embodiments, the porosity range of the porous polymer substrate is between about 20% to about 80% (for example, between about 28% to about 60%). The average pore size range of the porous polymer substrate is between about 0.02 μm to about 5 μm (for example, between about 0.08 μm to about 2 μm). In certain embodiments, the Gurley number range of the porous polymer substrate is between about 15 seconds to about 150 seconds. The porous polymer substrate can be or include one or more polyolefin polymers. The example of a suitable polyolefin polymer includes polypropylene, polyethylene or a combination thereof. In at least one aspect, the porous polymer substrate is a polyolefin film. In certain aspects, the polyolefin film is a polyethylene film or a polypropylene film.

[0039] Figure 2A cross-sectional view of one embodiment of a double-sided anode electrode structure 210 formed according to one or more embodiments described herein is shown. The double-sided anode electrode structure 210 includes an anode current collector 160 and anode films 170a, 170b (collectively, 170) formed on opposite sides of the anode current collector 160. The double-sided anode electrode structure 210 further includes one or more protective films 180a, 180b (collectively, 180) formed on the anode films 170a, 170b.

[0040] Figure 3 is a schematic cross-sectional view of a vapor deposition apparatus 300 comprising a roller 310. The vapor deposition apparatus 300 may be a roll-to-roll deposition system for coating flexible substrates, such as foils or polymer substrates. The thickness of the substrate to be coated may be 50 μm or less, in particular 20 μm or less, or even 6 μm or less. For example, a metal foil or a flexible metal-coated foil may be coated in the vapor deposition apparatus. In certain embodiments, the substrate 301 is a thin layer of copper foil or a thin layer of aluminum foil having a thickness of less than 30 μm, for example 6 μm or less. The substrate may also be a thin metal foil (e.g., copper foil) coated with graphite, silicon, silicon oxide, or any combination thereof, for example, with a thickness of 150 μm or less, in particular 100 μm or less, or even as low as 50 μm or less. According to certain embodiments, the coil may further comprise graphite, silicon, silicon oxide, or any combination thereof. For example, lithium may be pre-lithiated on a layer comprising graphite, silicon, silicon oxide, or any combination thereof.

[0041] In a roll-to-roll deposition system, the substrate 301 may be unwound from a storage roll, and as the substrate 301 is guided along a drum 310 , at least one or more material layers may be deposited on the substrate.

[0042] The drum 310 includes a curved surface 303 of the drum 310, a central axis A1, a first surface 311, and a second surface 309 opposite to the first surface 311. The drum 310 is rotatable around the central axis A1.

[0043] The vapor deposition apparatus 300 includes an evaporation unit 350 for depositing an evaporation material onto a substrate 301 according to the embodiments described herein. The evaporation unit 350 includes an evaporation crucible 330 for heating a solid or liquid source material 312 to a temperature exceeding the evaporation temperature or sublimation temperature of the source material 312, thereby evaporating the source material 312. The evaporation crucible 330 may include an interior space serving as a material reservoir for accommodating the source material 312 in a solid and / or liquid state, and a first heater 335 for heating the interior space of the evaporation crucible to evaporate the source material 312. For example, the source material 312 may be a metal, particularly lithium, and the first heater 335 may be configured to heat the interior space of the crucible to a temperature of approximately 180° C. or higher, particularly approximately 215° C. or higher, or approximately 400° C. or higher.

[0044] The evaporation unit 350 further includes a vapor distributor 320 having a plurality of nozzles 321 for directing evaporated material from the evaporation crucible toward the substrate 301 to deposit a coating on the substrate 301. The vapor distributor 320 may include an interior space that is in fluid communication with the interior space of the evaporation crucible 330, such that the evaporated material can flow from the interior space of the evaporation crucible 330 into the interior space of the vapor distributor 320 through a vapor conduit 340, for example, along a linear connecting pipe or channel. The plurality of nozzles 321 may be configured to direct the evaporated material from the interior space of the vapor distributor 320 toward the substrate 301.

[0045] In some embodiments, the vapor distributor 320 may be a vapor distribution showerhead having a plurality of nozzles arranged in a one-dimensional or two-dimensional pattern for directing vaporized material toward the substrate.

[0046] The evaporation crucible 330 is fluidly connected to the steam distributor 320 via a steam conduit 340 , which extends from the evaporation crucible 330 to the steam distributor 320 along the conduit length direction A. During the evaporation process, the temperature of the steam distributor 320 is generally set to a second temperature that is higher than the first temperature inside the evaporation crucible 330 to prevent material from condensing on the inner wall surface of the steam distributor.

[0047] The evaporation unit 350 may further include a second heater 325 for heating the inner space of the steam distributor. The first heater 335 and the second heater 325 can be controlled independently. For example, the first heater 335 can be configured to heat the evaporation crucible to a first temperature, and the second heater 325 can be configured to heat the steam distributor to a second temperature different from the first temperature, in particular higher than the first temperature. During the vapor deposition process, the inner space of the steam distributor is generally hotter than the inner space of the evaporation crucible to prevent the evaporated material from condensing on the inner wall of the steam distributor. On the other hand, the main inner space of the evaporation crucible should be maintained near the evaporation temperature of the source material 312 (i.e., slightly below or slightly above the evaporation temperature) so that the source material 312 is gradually evaporated at a predetermined evaporation rate.

[0048] In certain embodiments, which can be combined with other embodiments described herein, the plurality of nozzles 321 can be arranged in a plurality of nozzle rows extending along a row direction L and aligned with each other in a circumferential direction T, wherein the row direction L substantially corresponds to the axial direction of the drum 310. Thus, the steam distributor 320 provides an area showerhead having a plurality of nozzles arranged in a two-dimensional array to reduce the area heat load of the substrate 301 supported on the curved surface 303.

[0049] The substrate 301 is held on the curved surface 303 by an electrostatically adsorbed high voltage electrode and a dielectric coating located within the drum 310. The electrostatically adsorbed electrode and the dielectric coating can be integrated into the drum 310 in various embodiments depending on the type or material of the substrate.

[0050] Figure 4A A schematic diagram of a roll-to-roll unit 400 according to an embodiment of the present disclosure is shown, viewed along the central axis A1 of the drum 310. The roll-to-roll unit 400 may include an evaporation unit or a plurality of evaporation sources according to any embodiment described in this document, e.g. Figure 3 The evaporation unit 350 described in .

[0051] The roll-to-roll unit 400 includes a curved surface 303 of a roller 310 that serves as a substrate support, supporting the substrate 301 during the deposition process. The substrate 301 is supplied from a supply reel 401 to the roller 310, where material 315 is deposited onto the substrate 301. Once deposition is complete, the substrate 301 moves to a terminal reel 402, where it is wound around the terminal reel 402. Alternatively, the substrate 301 can proceed to other processing units for additional processing, such as additional deposition and / or coating processes in other equipment.

[0052] The plurality of nozzles 321 of the evaporation unit 350 are directed toward the curved surface 303, and the roll-to-roll unit 400 is configured to cause the substrate 301 to pass over the evaporation unit 350 on the curved surface 303. In some embodiments, a plurality of evaporation sources as described herein can be arranged sequentially in the circumferential direction T of the rotatable coating drum 310 so that the substrate can be coated subsequently by the plurality of evaporation sources. Different coating materials can be deposited on the substrate, or a thicker coating of the same coating material can be deposited on the substrate by the evaporation sources.

[0053] In certain embodiments, which can be combined with other embodiments described herein, the roll-to-roll unit 400 further includes an edge exclusion shield 411 extending from the roll-to-roll unit 400 to the curved surface 303 of the drum 310 .

[0054] The edge exclusion shield 411 shields the area of ​​the substrate 301 that does not need to be coated, for example, the side edge area of ​​the substrate to keep it free of coating material. For example, the edge exclusion shield 411 can be configured to shield two opposite edges of the substrate 301.

[0055] The edge exclusion shield 411 can extend along the curved surface 303 of the drum 310 in the circumferential direction T, following the curvature of the curved surface 303. Therefore, the gap width D between the curved surface 303 and the edge exclusion shield 411 can be kept small (e.g., 2 mm or less) and substantially constant in the circumferential direction T to improve the accuracy of edge exclusion and deposit a sharp and well-defined coating edge on the substrate 301.

[0056] like Figure 4A As shown, the roll-to-roll unit 400 includes a plurality of tension rollers. In certain embodiments, the roll-to-roll unit 400 includes a first tension roller 420 and a second tension roller 422. The first tension roller 420 receives the substrate 301 from the supply reel 401 and helps maintain tension on the substrate 301 as it passes through the drum 310. The substrate 301 moves from the drum 310 to the second tension roller 422. The second tension roller 422 helps maintain tension on the substrate 301 as it rolls around the drum 310. The substrate 301 moves from the second tension roller 422 to the end reel 402.

[0057] like Figure 4AAs shown, the evaporation unit 350 includes an evaporation crucible 330 for evaporating material, a steam distributor 320 with a plurality of nozzles 321 for directing the evaporated material to the substrate 301 supported on the drum 310, and a steam conduit 340 extending from the evaporation crucible 330 to the steam distributor 320 along the conduit length direction, providing a fluid connection between the evaporation crucible 330 and the steam distributor 320. The nozzle axis of at least one nozzle or all nozzles 321 may extend along the conduit length direction A or be substantially parallel to the conduit length direction. Figure 3 As shown, the conduit length direction A may substantially correspond to the radial direction of the drum 310 .

[0058] like Figure 4A As shown, the roller 310 includes a housing 430 and a cooling roller 410. The housing 430 is disposed radially outward of the cooling roller 410. The substrate 301 moves on an outer surface 433 of the housing 430. In some embodiments, the outer surface 433 of the housing 430 is a curved surface of the roller 310. In some embodiments, the housing 430 includes a dielectric coating with high thermal conductivity, such as cerium-doped aluminum nitride, which isolates a quasi-zero expansion coefficient thin metal electrode connected to a high voltage (e.g., >600 volts) DC power source, enabling the housing to act as an electrostatic chuck, adsorbing the substrate 301 with a thin (e.g., <15 microns) gap between the outer surface 433 and the substrate 301.

[0059] The curved outer surfaces of the housing 430 and the cooling drum 410 define a cavity 431. Cavity 431 may include narrow gas grooves spaced between the textured lands to allow gas to flow between the housing 430 and the cooling drum 410. The gas is then released from cavity 431 through slits in the housing 430. In some embodiments, the gas is pressurized to force the substrate 301 to move along the housing 430 on a cushion of air. In other embodiments, the gas acts as a heat transfer medium, cooling the substrate 301 by allowing heat to flow unimpeded through the gaps to the fluid-cooled housing 430. Because the gas is at a higher pressure, its thermal conductivity is higher, thereby enhancing the rate of thermal energy transfer. Cavity 431 is defined by the curved outer surface 444 of the housing 430 and the cooling drum 410. Supports 432 are located within cavity 431. Supports 432 extend from the curved outer surface 344 of the cooling drum 410 to the housing 430. In some embodiments, the cooling drum 410, support 432, and housing 430 are a single, integral component manufactured using additive manufacturing, such as metal additive manufacturing. In other words, the drum 310 is a single, integral drum. That is, the drum 310 is a single component formed using additive manufacturing. That is, the drum 310 is a single body formed using additive manufacturing. In some embodiments, portions of the drum 310 are formed using additive manufacturing. For example, the cooling drum 410 is a single, integral cooling drum formed using additive manufacturing.

[0060] The cooling drum 410 is partially defined by a curved outer surface 444 and an inner surface 440. The cooling drum 410 includes an outer region 443, a channel region 442, and an inner region 441. The outer region 443, the channel region 442, and the inner region 441 are disposed between the curved outer surface 444 and the inner surface 440. The cooling drum 410 is a single body. In other words, it is a single component. For example, the cooling drum 410 is a single 3D printed body. The cooling drum 410 is a metal drum with cooling channels ( Figure 4B ), these cooling channels are disposed within channel region 442 of cooling drum 410. Outer region 443 is disposed between curved outer surface 444 and channel region 442 of cooling drum 410. In one or more embodiments that may be combined with other embodiments, outer region 443 has a thickness between curved outer surface 444 and channel region 442 of about 0.1 mm to about 5 mm, such as about 1.5 mm in selective laser melting (SLM)-based additive manufacturing. This thickness is sufficient to reduce the risk of cavities between the molten pools, which could result in leakage of the heat transfer fluid. When outer region 443 is thinner, a greater rate of heat transfer can be achieved.

[0061] Channel region 442 is disposed between outer region 443 and inner region 441. Channel region 442 is disposed radially inward of outer region 443 and radially outward of inner region 441. In one or more embodiments that may be combined with other embodiments, the thickness of channel region 442 between outer region 443 and inner region 441 is approximately 0.1 mm to approximately 5 mm, for example, approximately 4 mm for selective laser melting (SLM) additive manufacturing-based embodiments. This thickness is selected to facilitate de-dusting. In one or more embodiments that may be combined with other embodiments, the thickness is approximately 1.3 mm for high-resolution lithographic printing, which can enhance local fluid velocity without causing excessively high pressure drop. The cross-sectional area of ​​fluid channel 460 is affected by the thickness of the channel region. Optimizing the hydraulic diameter or cross-sectional area gradient of fluid channel 460 aids in convective heat transfer efficiency and can ensure thermal uniformity across the exterior of cooling drum 410, enhancing deposition uniformity across substrate 301.

[0062] The passage region 442 includes at least one or more inlets 450. Although Figure 4A At least one or more inlets 450 are shown, including a first inlet 451, a second inlet 452, a third inlet 453, and a fourth inlet 454, but other embodiments are also contemplated. For example, there are embodiments with a single first inlet 451, embodiments with two inlets 450, embodiments with three inlets 450, embodiments with five inlets 450, embodiments with six or more inlets 450, but more inlets 450 are also contemplated. The inlets 450 are connected to the fluid channel 460 ( Figure 4B ).

[0063] The inlets 450 are radially disposed adjacent to the cooling drum 410. In some embodiments, the inlets 450 are positioned at approximately equal angular offsets from one another. For example, in an embodiment having four inlets, the inlets 450 are offset approximately 90° from one another. In other words, the inlets 450 may be radially arranged on the first surface 311 and / or the second surface 309.

[0064] Figure 4B The internal geometry of the channel region 442 is shown according to certain embodiments.While previous manufacturing methods have been unable to create internal spiral structures within a component, various forms of additive manufacturing have enabled cooling drums to have internal spiral cavities, as described herein.

[0065] Inlet 450 is connected to and in fluid communication with fluid channels 460. In certain embodiments, fluid channels 460 include a first fluid channel 461, a second fluid channel 462, a third fluid channel 463, and a fourth fluid channel 464. Although only four fluid channels 460 are shown, other numbers are contemplated, including one fluid channel 460, two fluid channels 460, three fluid channels 460, six fluid channels 460, or six or more fluid channels 460.

[0066] The first fluid channel 461 is connected to the first inlet 451 and is in fluid communication. The first inlet 451 is located near the first surface 311. The first fluid channel 461 is partially composed of an outer region 443 and an inner region 441 ( Figure 4A ) definition. The first fluid channel 461 forms a spiral channel around the central axis A1 of the cooling drum 410 ( Figure 4A ). The first fluid channel 461 is connected to and connected to a first outlet 471 of at least one or more outlets 470. The first outlet 471 is provided on the second surface 309 of the cooling drum 410 ( Figure 4A ).

[0067] The second fluid channel 462 is connected to the second inlet 452 and is in fluid communication. The second inlet 452 is located near the first surface 311. The second fluid channel 462 is composed of an outer region 443 and an inner region 441 ( Figure 4A ) definition. The second fluid channel 462 forms a spiral channel around the central axis A1 of the cooling drum 410 ( Figure 4A The second fluid channel 462 is connected to the second outlet 472 of at least one or more outlets 470. The second outlet 472 is provided on the second surface 309 of the cooling drum 410 ( Figure 4A ).

[0068] The third fluid channel 463 is connected to the third inlet 453 and is in fluid communication. The third inlet 453 is close to the first surface 311. The third fluid channel 463 is partially defined by the outer region 443 and the inner region 441. Figure 4A The third fluid channel 463 forms a spiral channel around the central axis A1 of the cooling drum 410 ( Figure 4A The third fluid channel 463 is connected to the third outlet 473 of at least one or more outlets 470. The third outlet 473 is provided on the second surface 309 of the cooling drum 410 ( Figure 4A ).

[0069] The fourth fluid channel 464 is connected to the fourth inlet 454 and is in fluid communication. The fourth inlet 454 is adjacent to the first surface 311. The fourth fluid channel 464 is partially defined by the outer region 443 and the inner region 441 ( Figure 4AThe fourth fluid channel 464 forms a spiral channel around the central axis A1 of the cooling drum 410 ( Figure 4A The fourth fluid channel 464 is connected to the fourth outlet 474 of at least one or more outlets 470. The fourth outlet 474 is provided on the second surface 309 of the cooling drum 410 ( Figure 4A ).

[0070] In some embodiments, two inlets 450 are disposed on the first side 311, and another two inlets 450 are disposed on the second side 309. In this embodiment, two outlets are disposed on the first side 311, and another two outlets 470 are disposed on the second side 309. By configuring the inlets and outlets on both sides 309 and 311, the cooling drum can achieve relative cooling fluid flow, achieving uniform cooling across the entire drum.

[0071] In some embodiments, the fluid outlet 470 of the fluid channel 460 is disposed near the second face 309. In some embodiments, the fluid inlet 450 of the fluid channel 460 is disposed near the first face 311.

[0072] Fluid outlets 470 are radially arranged on the cooling drum 410. In some embodiments, the fluid outlets 470 are arranged with equal angular offsets. For example, in an embodiment having four outlets, the angular offsets between the fluid outlets 470 are approximately 90°. In other words, the fluid outlets 470 can be radially arranged on the first surface 311 and / or the second surface 309.

[0073] In some embodiments, fluid channel 460 has a uniform number of rotations per unit length. For example, fluid channel 460 may have one rotation per 100 millimeters around central axis A1. In other words, for every 800 millimeters of central axis A1, each fluid channel 461, 462, 463, 464 may have approximately 1 to approximately 20 rotations around central axis A1. In other embodiments, the number of rotations per unit length of fluid channel 460 may vary. For example, the number of rotations per unit length around central axis A1 may increase or decrease along central axis A1.

[0074] The fluid channels 460 are offset from one another. For example, the first fluid channel 461 is offset from the second fluid channel 462. The fluid channels 460 are radially offset to a certain extent so that they do not intersect. In other words, the inlet 450 is radially distributed around the central axis A1 so that the fluid channels 460 are evenly offset from one another in the radial direction.

[0075] Figure 4C is a partial schematic cross-sectional view of the drum 310 taken according to certain embodiments, the figure is taken along Figure 4BAs shown in the figure, each fluid channel 460 forms a parallel spiral channel in the cooling drum 410. As shown in the figure, the substrate 301 receives gas from a plurality of gas slits 480. The slits 480 are openings on the outer surface 433 of the housing 430. The gas is supplied to the cavity 431 through a gas inlet 481. According to certain embodiments, the gas inlet 481 is provided on the first surface 311. In certain embodiments, there are a plurality of gas inlets 481. In certain embodiments, there is also a gas inlet on the second surface 309. In certain embodiments, there are gas inlets on both the first surface 311 and the second surface 309.

[0076] As the substrate 301 receives thermal energy during operation, the thermal energy is transferred from the substrate to the gas. The thermal energy is then transferred from the gas to the outer surface 444 of the cooling drum 410. To further remove thermal energy from the substrate 301, a coolant is flowed through the fluid channels 460 to maintain the temperature of the substrate 301 below 180.5°C, which is approximately the melting point of lithium. More specifically, the temperature of the substrate 301 is maintained below 70°C, which is the glass transition or softening temperature of the polymer binder in some anodes. For example, below 10°C, which is the typical operating set point for commercial water-glycol heat exchangers. For example, below -30°C when using silicone oil heat exchangers for high-throughput lithium coil coating.

[0077] The spiral shape of fluid channel 460 enhances the amount of heat removed by the coolant through secondary circulation. The spiral design, achieved through additive manufacturing, allows for a smaller distance 483 between substrate 301 and fluid channel 460. For example, distance 483 between fluid channel 460 in channel region 442 and substrate 301 ranges from approximately 1 mm to approximately 10 mm. Distance 483 between fluid channel 460 in channel region 442 and substrate 301 includes the radial thickness of outer region 443, the radial thickness of cavity 431, the radial thickness of outer shell 430, and any gap formed between substrate 301 and outer shell by gas cushion 484. The thickness of gas cushion 484 is defined by the radial thickness between outer shell 430 and substrate 301. In certain embodiments, the thickness of the gas cushion ranges from approximately 1 micron to 110 microns, for example, less than 80 microns.

[0078] In certain embodiments, substrate 301 moves along housing 430 without being separated by a cushion of gas. When not separated by a cushion of gas, housing 430 further enhances heat removal through conduction. Therefore, by additively manufacturing the entire roller 310 using materials with high heat transfer coefficients, greater cooling can be achieved. For example, by forming the roller using aluminum, copper, copper alloys, aluminum alloys, aluminum materials, and / or materials containing copper, substrate 301 can be cooled more effectively. Other materials with heat transfer coefficients are also contemplated to improve the heat transfer rate from substrate 301 to cooling roller 410.

[0079] Figure 5A and Figure 5B A view of the interior of a fluid channel 460 is schematically shown according to certain embodiments. The fluid channel 460 includes surface features 501. Figure 5A A cross-sectional view of the fluid channel 460 relative to fluid flow is schematically illustrated according to certain embodiments.

[0080] The surface features 501 may be located on an outer radial surface 503 between the outer region 443 and the channel region 442. The surface features 501 may be located on an inner radial surface 505 between the inner region 441 and the channel region 442. The surface features 501 may be located on one or more sidewalls 507 in the channel region 442.

[0081] Figure 5B A cross-sectional view of the fluid channels 460 is schematically illustrated according to certain embodiments. The inner radial surface 505 , the outer radial surface 503 , and the sidewall 507 of the interior surface 510 of each fluid channel 460 .

[0082] like Figure 5B As shown, fluid channel 460 has a rectangular shape according to some embodiments. In some embodiments, fluid channel 460 has a trapezoidal shape. In some embodiments, fluid channel 460 has a circular shape. In some embodiments, fluid channel 460 forms a porous lens shape.

[0083] The surface feature 501 can be a spoiler and / or a spoiler surface feature. For example, the surface feature 501 can be a wavy spoiler and / or a spoiler wavy surface feature configured to prevent laminar flow. The use of additive manufacturing technology can add wavy high surface area periodic spoiler features to the internal surface 510 while keeping the distance that heat energy needs to be transferred to a minimum. The metal additive manufacturing of the drum 310 produces a porous three-dimensional wavy structure, which serves as a heat exchanger spoiler for the cooling drum 410, thereby enhancing the cooling capacity of the drum 310. The surface feature 501 prevents the formation of such a structure in the fluid channel 460 by accelerating the flow rate of the coolant. Figure 3The uniform gradient in the L direction is shown. This acceleration is caused by reducing the hydraulic diameter or cross-sectional area of ​​the fluid channel 460. By increasing the wetted surface area involved in heat transfer, heat is extracted from the housing 430 along the length of the fluid channel 460 through the gradient modulation of the surface features 501, thereby improving the heat transfer of the fluid. The surface features 501 enhance the cooling capacity of the fluid channel 460 by compensating for increases in the coolant flow temperature to provide a uniform fluid channel 460 temperature, thereby forcing a uniform and large temperature difference between the outer radial surface 503 and the outer region 443. The optimized spoiler geometry reduces the uniform coolant flow within the fluid channel, thereby compensating for the increased oil temperature gradient. By reducing the thermal gradient within the fluid channel, the roller surface temperature is more uniform, and the non-uniformity of the substrate coating is reduced.

[0084] Surface features 501 cause the flow of the coolant to be non-laminar. For example, surface features 501 cause the flow of the coolant to have a Reynolds number between about 2300 and about 4000. For example, when the coolant flows at a speed of about 0.5 meters per second to about 5 meters per second (e.g., 1 meter per second), surface features 501 cause the flow of the coolant to have a Reynolds number between about 2300 and about 4000.

[0085] Figure 6 A method 600 for cooling a substrate when using a roll-to-roll deposition system is described. In operation 601, a cooling liquid is supplied to the fluid channels 460 within the cooling drum 410 of the drum 310. As the cooling liquid flows through the first fluid channels 461, the cooling liquid is disturbed to achieve a uniform temperature distribution perpendicular to the flow of the cooling liquid.

[0086] In operation 603, a gas is supplied to the cavity 431 of the drum 310. The gas can be an inert gas. For example, the gas is argon. For example, the gas is carbon dioxide. Other gases are also contemplated.

[0087] In operation 605, an evaporation unit deposits a material onto substrate 301. The material may be a lithium anode material. In certain embodiments, the material may be a lithium material deposited onto a polymer substrate having a graphite layer for pre-lithiation.

[0088] The previously described embodiments of the present disclosure have many advantages, including the following. The apparatus is capable of vacuum coil coating at a heat load of 50,000 watts per square meter with a temperature difference between the drum surface and the coolant channels of less than 35°C and a transverse drum surface temperature non-uniformity of less than 4°C. The present disclosure provides lithium deposition rates ranging from about 5 microns per minute to about 60 microns per minute, or greater than 60 microns per minute, suitable for transfer lamination and lithium-ion battery anode coils. For example, the present disclosure provides lithium deposition rates on transfer lamination and lithium-ion battery anode coils of about 10 microns per minute to about 20 microns per minute. However, the present disclosure does not require that all advantageous features and advantages be incorporated into every embodiment.

[0089] The present disclosure increases the heat transfer surface area of ​​the cooling channels and reduces the thickness of the boundary layer to promote high deposition rates and low deposition thickness non-uniformity, thereby improving coating economy and yield. The roller utilizes metal additive manufacturing technology to produce an optimized porous three-dimensional cubic geometry as a heat exchanger spoiler integrated with the cooling roller. A gas, such as an inert gas, is dispersed between the cooling roller and the shell. The cooling roller and / or the shell can be additively manufactured. The cooling roller assembly also includes a bulk flow fluid manufactured by additive manufacturing to increase the cooling rate. The optimized spoiler geometry reduces the uniformity of the coolant flow in the fluid channel, thereby compensating for the gradient increase in oil temperature. By reducing the thermal gradient in the fluid channel, the roller surface temperature is more uniform and the non-uniformity of the substrate coating is minimized. In the additive manufacturing process, copper alloys or aluminum alloys can be used to form the roller. A roller for vapor deposition is shown and described herein. A vapor deposition apparatus having a roller is shown and described herein. A method for coating a substrate is shown and described herein.

[0090] While the foregoing is directed to certain embodiments, other further embodiments may be devised without departing from the basic scope, which is determined by the following claims.

Claims

1. A roller for vapor deposition, comprising: a housing having a gas slit; as well as A cooling drum, comprising: External areas; Internal area; a first fluid passage, the first fluid passage being defined in part by the outer region and the inner region, the first fluid passage forming a spiral passage about a central axis of the cooling drum; and A first inlet is in fluid communication with a first outlet through the first fluid passage. 2 . The drum according to claim 1 , wherein the cooling drum is a single-piece drum made of copper or aluminum alloy. The drum of claim 1 , wherein the first fluid channel comprises a flow-disturbing surface feature.

4. The drum of claim 1 , wherein the cooling drum further has a second fluid channel radially offset from the first cooling channel, and the second fluid channel is partially defined by the outer region and the inner region, the second fluid channel forming a spiral channel around the central axis of the cooling drum. 5 . The drum as claimed in claim 4 , wherein the second fluid channel connects the second fluid inlet to the second fluid outlet.

6. The drum of claim 4, wherein the first inlet and the second inlet are disposed in a first face of the cooling drum.

7. The drum of claim 4, wherein the first inlet and the second outlet are disposed in a first side of the cooling drum, and the second inlet and the first outlet are disposed in a second side of the cooling drum.

8. The drum of claim 1, wherein a distance between the outer shell and a curved surface of the outer region of the cooling drum is between about 1 mm and about 5 mm.

9. The drum of claim 1, wherein the first inlet is located adjacent a first side of the cooling drum and the first outlet is located adjacent a second side of the cooling drum, the second side being separated by a curved surface of the cooling drum.

10. The drum of claim 1, wherein the outer region has a thickness of less than 10 mm.

11. A roll-to-roll deposition system, comprising: Evaporation unit; Multiple tension rollers; as well as A roller, the roller being located between the plurality of tension rollers and the evaporation unit, the roller comprising: a housing having a gas slit; and A cooling drum, comprising: External areas; Internal area; a first fluid passage, the first fluid passage being defined in part by the outer region and the inner region, the first fluid passage forming a spiral passage about a central axis of the cooling drum; and A first inlet is in fluid communication with a first outlet through the first fluid passage.

12. The roll-to-roll deposition system of claim 11, wherein the cooling drum is integral and made of copper or aluminum alloy.

13. The roll-to-roll deposition system of claim 11 , wherein the cooling drum further comprises a second fluid channel radially offset from the first cooling channel, the second fluid channel being partially defined by the outer region and the inner region, and the second fluid channel forming a spiral channel around the central axis of the cooling drum.

14. The roll-to-roll deposition system of claim 13, wherein the first inlet and the second inlet are disposed on a first side of the cooling drum.

15. The roll-to-roll deposition system of claim 13, wherein the first inlet is disposed on a first side of the cooling drum, and the second inlet is disposed on a second side of the cooling drum.

16. The roll-to-roll deposition system of claim 11, wherein the first fluid channel comprises a flow-disrupting surface feature.

17. A method of applying an anode material to a substrate, the method comprising: Cooling liquid is supplied to a drum comprising: housing; and a cooling drum, the cooling drum being radially inwardly disposed within the housing, the cooling drum having a first fluid passage, the first fluid passage being partially defined by an outer region of the cooling drum and an inner region of the cooling drum, the first fluid passage forming a spiral passage around a central axis of the cooling drum, the first fluid passage having a turbulent surface feature; flowing a coolant through the first fluid passage; flowing gas through a cavity between the housing and the cooling drum; unfolding a substrate onto the housing; and Anode material is evaporated onto the substrate.

18. The method of claim 17, wherein the cooling liquid flows at a speed of less than 1 meter per second.

19. The method of claim 17, wherein a gas cushion is formed between the substrate and the housing, the gas escapes from the housing through a plurality of gas slits, and the gas cushion is less than 15 microns.

20. The method of claim 17, wherein the flow of the cooling liquid has a Reynolds number of about 2300 to about 4000.

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