Solution phase deposition of thin films on solid state electrolytes

Abstract

Methods, systems, and compositions for solution-phase deposition of thin films comprising one or more artificial solid electrolyte interface (SEI) layers. The thin films can be coated onto the surface of porous components of electrochemical instruments, such as solid electrolytes for rechargeable battery packs. The methods and systems provided herein relate to exposing the component to be coated to different liquid reagents in sequential processing steps, optionally including rinsing and drying steps. The processing can occur in a single reaction chamber or multiple reaction chambers.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 62 / 936,609, filed November 18, 2019, which is incorporated herein by reference for all purposes. Technical Field

[0003] Embodiments of this disclosure generally relate to methods and systems for coating thin films onto the surface of solid electrolytes for rechargeable battery packs. Background Technology

[0004] Solid ceramic, solid inorganic, or solid polymer electrolytes offer numerous advantages over their liquid counterparts when used as ion transfer media in rechargeable battery packs. For example, the significantly reduced (or eliminated) flammability of solid electrolytes compared to existing technologies provides greatly improved safety for the resulting battery packs. Solid electrolytes typically exhibit enhanced electrochemical stability compared to liquid electrolytes, enabling battery packs made with solid electrolytes to operate over a wider voltage range.

[0005] However, solid electrolytes present numerous interface problems when used in conjunction with standard rechargeable battery pack electrodes. For example, when paired with lithium-ion battery pack electrodes, the interface between the solid electrolyte and adjacent electrodes typically increases ionic resistance, thereby reducing the battery pack power density. These interfaces can also inhibit adequate wetting between the electrodes and the electrolyte and may lead to the formation of undesirable secondary phases due to thermodynamic instability.

[0006] Therefore, it is necessary to improve the electrode / electrolyte interface in rechargeable battery packs made with solid electrolytes in a way that mitigates these aforementioned problems.

[0007] Recent research has attempted to improve solid electrolyte / electrode interfaces by applying thin film coatings deposited by atomic layer deposition (ALD). Coatings applied via ALD have been shown to improve electrode material wetting, reduce impedance, and decrease detrimental side reactions typically associated with capacity decay.

[0008] Traditional atomic layer deposition (ALD) technology relies on the evaporation of metal-organic precursors in a vacuum chamber; a substrate placed within this chamber is exposed to a turbulent flow of metal-organic vapors. The substrate surface reacts with the turbulent vapors to precisely produce a self-confined, surface-saturated monolayer of adsorbed metal-organic material. In one example, metal-organic material is adsorbed, and excess metal-organic material is subsequently purged using a vacuum and inert gas, followed by exposure of the substrate surface to an oxidant (e.g., H₂O, O₂, or O₃) resulting in the precise formation of a monolayer of metal oxide.

[0009] ALD is particularly well-suited for producing conformal coatings with precise thicknesses on substrates with porous microstructures, such as solid electrolyte matrices. Substrates with this morphology typically cannot be adequately coated by other physical vapor deposition (PVD) methods, such as sputtering, due to line-of-sight limitations. To conformally and uniformly coat all surfaces within the porous morphology, a deposition technique similar to ALD is required, where a considerable amount of time is allowed for surface flow of adsorbed atoms prior to reaction. However, many manufacturing limitations of conventional ALD methods highlight the need for a more fabricatable method to achieve similar film quality, uniformity, and conformability.

[0010] While organometallic reagents (i.e., precursors) used in ALDs of oxides (e.g., Al₂O₃ and ZnO) (trimethylaluminum (TMA) and diethylzinc (DEZ), respectively) evaporate at relatively low temperatures (<100 °C) and moderate base vacuum pressures (>1 Torr), most organometallic precursors require temperatures above 100 °C (and many above 200 °C) to produce significant vapor pressures. A key drawback of the high precursor boiling points is that the substrate temperature must also be maintained above the precursor boiling points to prevent precursor condensation on the substrate surface. Precursor condensation leads to a loss of monolayer-to-monolayer growth control, which in turn results in unpredictable final film thickness. Due to the lack of a heat transfer medium, the substrate in the evacuated ALD chamber often also requires radiative heating (e.g., suspended roll-to-roll foil substrates). Radiative heating is inefficient for reflective foil substrates (e.g., those used for battery pack electrodes). Residual gas trapped within the layers of roll-to-roll substrates can prolong evacuation time in conventional ALD chambers, and unused precursors result in poor material utilization in conventional ALD methods due to losses from continuous cleaning and evacuation. The auto-ignition properties of gaseous organometallic precursors typically used in conventional ALD methods also necessitate the integration of expensive safety infrastructure.

[0011] For decades, high-quality conformal thin films of oxides and chalcogenides have been deposited on porous substrates using techniques other than ALD (Alternating Layer Deposition), such as chemical bath deposition (CBD), sequential ion layer adsorption and reaction (SILAR), and layer-by-layer sol-gel. In CBD, an aqueous solution of a complexed metal precursor is typically mixed with a chalcogenide or oxide ion source. These methods are generally performed at moderate temperatures, well below the decomposition temperatures of the cell electrode materials, binders, or separators. CBD is well-known for depositing high-quality CdS or ZnS as n-type junction partners on CdTe or CIGS thin-film solar cells. This technique has been used for many years, setting world records for the efficiency of these types of solar cells. They produce high open-circuit voltages, high diode ideality, and high shunt resistance, indicating excellent film quality and conformability. CBD methods have also been commercialized in high-capacity thin-film solar cell production lines.

[0012] A useful variant of CBD technology is SILAR. In this case, the substrate is alternately exposed to solutions of cationic and anionic reactants, with rinsing steps in between. While this technique results in slower film growth, its benefit lies in the elimination of homogeneous nucleation (precipitation) from the mixing of the two reactants, which significantly improves material utilization. Given that the tunneling limit of good dielectrics is on the order of 1–2 nm, SILAR technology is feasible for depositing passivation layers on solid electrolyte surfaces. Thickness control in the SILAR method is also better than in the CBD method; for example, thickness control of the passivation layer on solid electrolytes is crucial for preventing undesirable barriers to lithium diffusion while maintaining the electron tunneling barrier.

[0013] Solution-based techniques also exist that utilize the same types of organometallic compounds used in gas-phase ALD to demonstrate layer-by-layer sol-gel coating. For example, an Al₂O₃ monolayer can be grown by immersing a substrate in a suitable aluminum alkoxide solution. Adsorption of the organometallic precursor followed by an oxidation step (e.g., hydrolysis) produces an oxide monolayer. These steps are repeated, with rinsing steps in between, to produce monolayer-to-monolayer coatings. The metal alkoxide precursors are typically soluble to very high molar concentrations in standard organic solvents such as 2-propanol. In recent years, high-quality Al₂O₃, SiO₂, and ZrO₂ composite barrier layers have been grown on TiO₂ dye-sensitized solar cells using this technique. Similar techniques have also been used to deposit various polymer materials, such as "metalcone" and polyamides.

[0014] US PGPUB 2016 / 0090652 proposes a liquid-phase ALD method similar to the one described above, in which a discrete wafer substrate is continuously exposed to a solution of a metal-organic precursor, a rinsing solvent for removing excess metal-organic compounds, an oxidizing solution, and another rinsing. These four steps are repeated to produce a film of any desired thickness. The wafer is attached to a spin-coating apparatus; after each step, the wafer is immediately rotated to remove excess fluid. While this technique works well for wafer-like substrates, it cannot be used to coat continuous substrates, such as foil rolls. Furthermore, spin-coating systems can only coat individual discrete substrates with lateral dimensions up to several hundred millimeters. Coating larger substrates via spin-coating is also impractical due to practical mechanical limitations. Coating uniformity also decreases with increasing substrate size.

[0015] Therefore, there is a need for economical coating of porous, discrete substrates. While conventional ALD techniques have been proven on a large scale for coating certain discrete substrates (e.g., wafers), they often suffer from the same manufacturability limitations as with continuous substrates, as described above. This is especially true when the target coating material requires expensive precursors, and poor material utilization in ALD makes the approach economically unfeasible.

[0016] In this context, an example of a discrete porous substrate that can be more economically coated using solution phase deposition techniques is a freestanding solid electrolyte, such as a ceramic solid electrolyte. An example of a ceramic solid electrolyte frequently processed into freestanding, discrete, sintered granules or plates is Li7La3Zr2O. 12 (LLZO). Then, anode and cathode materials are typically applied to either side of the freestanding electrolyte to produce a solid-state battery pack.

[0017] However, to meet the demands of large-scale applications (such as consumer electronics, electric vehicles, or grid-scale energy storage), the size of rechargeable battery packs is often altered to adopt a roll-to-roll (R2R) manufacturing process. This involves large rolls of foil current collectors being processed at high speed and continuously through various manufacturing steps to produce battery pack electrode rolls, which are then cut and diced into individual cells. This manufacturing method results in a significant amount of GWh of lithium-ion battery packs produced globally each year. Therefore, to change the size of solid-state battery packs to meet the demands of these large-scale applications without interfering with the (mature) R2R battery pack manufacturing method, R2R manufacturing techniques should also be used to apply solid-state electrolytes. One example is a solid ceramic electrolyte with a standard lithium-ion cathode material (e.g., LiNi). x Mn y Co z The co-sintering of O2 produces a bulk powder, which can then be cast onto a current collector using standard adhesives and conductive binders. In another example, a solid polymer electrolyte can be fabricated as a freestanding membrane and then “sandwiched” between sheets of anode and cathode before being assembled into a battery, all as part of an embedded R2R method.

[0018] Unfortunately, due to many of the aforementioned methodological constraints, in addition to high upfront capital costs and slow processing times, the R2R vapor-phase ALD method for applying coatings to solid electrolytes or solid electrolyte-electrode composites in lithium-ion manufacturing processes is unsustainable.

[0019] Therefore, the purpose of this disclosure is to meet the above-mentioned needs by applying a coating to the solid electrolyte / electrode interface and to provide other benefits, such as the use of a manufacturing method that is less expensive and more scalable than ALD, which can also be extended to R2R form. Summary of the Invention

[0020] The systems and methods disclosed herein provide a way to deposit a thin film coating in the form of an artificial solid electrolyte interface (SEI) layer on the surface of a substrate, such as a battery pack electrode, a solid electrolyte, or a solid electrolyte / electrode composite. The methods disclosed herein enable battery packs to have a solid electrolyte and are more commercially and technically feasible for introduction into the manufacture of high-capacity lithium-ion battery packs (LIBs) compared to roll-to-roll or discrete vapor phase ALD or other high-vacuum vapor phase deposition methods.

[0021] In particular, in some aspects, liquid phase deposition methods and systems for coating thin films containing artificial SEIs onto substrates are provided. In some embodiments, the substrate is a continuous substrate having an aspect ratio of at least 10:1 between its two largest dimensions and being sufficiently flexible to be wound onto itself in a roll. In some embodiments, the substrate is a discrete substrate having an aspect ratio of <10:1 between its two largest dimensions and / or having a length dimension of at least 100 mm and being sufficiently rigid to require handling as discrete units.

[0022] The methods and systems disclosed herein facilitate precise control over the thickness and conformability of desired artificial SEI films by allowing reagents (i.e., precursors) to adsorb and move across the substrate surface, as in ALDs, although via liquid-phase delivery rather than gas-phase delivery. The liquid-phase delivery of the reagents disclosed herein utilizes solvation energy to move the reagents, rather than relying on the high-temperature thermal evaporation of current production methods. Another advantage of this disclosure is the difference in specific heat capacity of the solvents used, which can also serve as a medium for both heat transfer and precursor transfer, resulting in faster and more efficient substrate heating. The precursors dissolved in solution are also significantly more stable in terms of exposure to air compared to their pure analogues, resulting in improved safety and easier handling.

[0023] Therefore, in a basic embodiment, this disclosure provides a method for coating a thin film comprising an artificial SEI onto a continuous substrate, the method comprising:

[0024] (a) In a first reaction chamber, the continuous substrate is exposed to a first liquid solution containing at least a first reagent to produce a layer containing the absorbed first reagent on the continuous substrate, and excess first reagent is rinsed off from the substrate surface, subsequently...

[0025] (b) In a second reaction chamber, the continuous substrate from step (a) is exposed to a second liquid solution containing at least a second reagent, wherein the second reagent reacts with the first absorbed reagent to produce a monolayer film containing the artificial SEI coated onto the continuous substrate, the artificial SEI containing a compound generated by the reaction of the second reagent and the absorbed first reagent, and then excess of the second reagent is rinsed off from the substrate surface.

[0026] Continuous substrates are commonly used in electrochemical instruments, such as battery packs, and in some embodiments, they consist of flexible foil current collectors coated with a composite matrix of a solid electrolyte and electrode materials. In some embodiments, the continuous substrate consists of a flexible foil current collector coated with electrode materials (i.e., without electrolyte). In other embodiments, the continuous substrate can be a continuous film of a solid polymer-electrolyte. In some embodiments, the foil current collector contains a metal. In some embodiments, the metal is Cu, Al, or stainless steel.

[0027] In some embodiments, the electrode material comprises one or more of the following: graphite, Si, Sn, Ge, Al, P, Zn, Ga, As, Cd, In, Sb, Pb, Bi, SiO, SnO2, Si, Sn, lithium metal, LiNi x Mn y Co z O2, LiNi x Co y Al z O2, LiMn x Ni y O z LiMnO2, LiFePO4, LiMnPO4, LiNiPO4, LiCoPO4, LiV2O5, sulfur or LiCoO2, where x, y and z are stoichiometric coefficients.

[0028] In some embodiments, the freestanding solid electrolyte or the solid electrolyte within a composite matrix of solid electrolyte and electrode material comprises one of the following: Li w La x M y O 12 (where M is Nb, Ta, or Zr), Li x MP y S z (where M is Ge or Sn), Li w Al x M y (PO4)3 (where M is Ge or Ti), Li x Ti y M z (PO4)3 (where M is Al, Cr, Ga, Fe, Sc, In, Lu, Y, or La) or Na x Zr2Si y PO 12 In all cases, x, y, and z represent stoichiometric coefficients. In some embodiments, the solid electrolyte is processed into freestanding, discrete, sintered granules or plates. In some embodiments, the solid electrolyte is Li7La3Zr2O.12 (LLZO).

[0029] In some embodiments, the electrode material consists of an active material and other constituent materials (e.g., adhesive binders and conductive additives), the active material being a portion of the electrode that is inserted into or extracted from lithium during charging / discharging.

[0030] In some embodiments, the continuous substrate is a solid polymer film composed of one or more of the following polymers: polyethylene oxide (PEO), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), polydimethylsiloxane (PDMS), and polyvinylpyrrolidone (PVP). When combined with lithium salts (e.g., especially LiClO4, LiPF6, or LiNO3), such polymers can produce solid polymer electrolyte films.

[0031] In some embodiments, a thin film containing an artificial SEI is coated onto a rigid discrete substrate by a method including the following steps:

[0032] (a) Exposing the discrete substrate to a first liquid solution containing at least a first reagent in a first reaction chamber to produce a layer containing the absorbed first reagent on the continuous substrate, followed by rinsing off excess first reagent from the surface of the substrate, and

[0033] (b) In a second reaction chamber, the discrete substrate from step (a) is exposed to a second liquid solution containing at least a second reagent, wherein the second reagent reacts with the first absorbed reagent to produce a monolayer film containing the artificial SEI coated onto the continuous substrate, the artificial SEI containing a compound generated by the reaction of the second reagent and the absorbed first reagent, and then excess of the second reagent is rinsed off from the substrate surface.

[0034] In some embodiments, the discrete substrate is a freestanding sintered pellet or plate of a solid electrolyte, comprising one of the following materials: Li w La x M y O 12 (where M is Nb, Ta, or Zr), Li x MP y S z (where M is Ge or Sn), Li w Al x M y (PO4)3 (where M is Ge or Ti), Li x Ti y M z (PO4)3 (where M is Al, Cr, Ga, Fe, Sc, In, Lu, Y, or La) or Na xZr2Si y PO 12 In all cases, x, y, and z represent stoichiometric coefficients.

[0035] In some embodiments, the conveying device may be a roll-to-roll deposition system. In some embodiments, the conveying device includes a series of rollers for guiding the substrate into the deposition chamber. In some embodiments, the conveying device includes a track through which discrete substrates are conveyed from one deposition chamber to the next.

[0036] In some embodiments, the method further includes exposing the coated continuous or discrete substrate to heat treatment in the presence of an environment containing a defined gas composition. In some embodiments, these gases may be a mixture of O2, ozone, N2, and Ar. In some embodiments, the coated substrate may be heated to temperatures up to 1000°C in the presence of the gas. In some embodiments, the coated substrate may be heated while being exposed to a plasma containing oxygen, argon, hydrogen, or nitrogen.

[0037] The first liquid solution comprises at least a first reagent. The first reagent can be any compound capable of reacting with a material of the continuous substrate to form a self-confining layer on the continuous substrate. In some embodiments, the first reagent is an organometallic compound. Examples of such organometallic compounds include, but are not limited to, aluminum trisec-butoxide, titanium ethoxide, niobium ethoxide, trimethylaluminum, and zirconium tert-butoxide. In another embodiment, the first reagent comprises an aqueous solution containing an ionic compound. Examples include, but are not limited to, zinc acetate, cadmium chloride, zinc chloride, zirconium chloride, and zinc sulfate. In some embodiments, the pH of the first solution can be varied.

[0038] In embodiments where the first reagent is an organometallic compound, the first liquid solution may further contain a solvent for dissolving or complexing the first reagent. Preferred solvents include organic solvents, such as alcohols (e.g., isopropanol or ethanol), alcohol derivatives (e.g., 2-methoxyethanol), slightly less polar organic solvents (e.g., pyridine or tetrahydrofuran (THF)), or nonpolar organic solvents (e.g., hexane and toluene).

[0039] The first liquid solution is contained within the first reaction chamber. The reaction chamber can be any apparatus suitable for performing step (a). Therefore, the reaction chamber must be large enough to receive the continuous substrate and to hold the amount of liquid solution to be used. Such apparatus that can be used as a reaction chamber includes, but is not limited to, tanks, baths, pans, beakers, etc.

[0040] After the first layer adsorbs onto the continuous substrate in step (a), unreacted reagents and excess solvent are typically retained on the substrate. To remove these compounds, the continuous substrate may undergo an optional rinsing or washing step. In this step, the substrate is rinsed with a first rinsing solution containing a solvent, which removes unwanted and unreacted compounds from the continuous substrate. The rinsing step leaves exactly a saturated (i.e., purified) first layer on the substrate that may be directed to step (b) of the method, and leaves a residual solution containing the first solvent and unreacted first reagent in the reaction chamber.

[0041] As an optional step, to recover the solvent and any unreacted reagents used in the rinsing step, the residual solution can be passed to a filtration step. The filtration step separates the solvent from the unreacted reagents (and any reaction byproducts). The filtration step also prevents cross-contamination between chambers and avoids slow contamination of the rinsing solution by reagents during operation. A continuous filtration rinsing bath not only maintains the purity of the rinsing solvent but can also be used as a material recovery system, thereby improving the material utilization efficiency of the method. Any filtration technique known in the art can be used. Preferred techniques include, but are not limited to, membrane separation, chemical precipitation, ion exchange, electrochemical removal, physical adsorption, and flow filtration chromatography.

[0042] The separated solvent can be recycled back to the rinsing step for reuse. Similarly, the filtered unreacted first reagent can be recycled back to step (a) for further use in the method.

[0043] The resulting continuous substrate, having a layer containing the adsorbed first reagent, is then fed to step (b). Here, in a manner similar to step (a) above, the continuous substrate is exposed to a second liquid solution containing the second reagent in a second reaction chamber. In some embodiments, the second liquid solution will contain an oxidizing agent, such as an oxide or sulfide source, examples of which include, but are not limited to, water, thiourea, and sodium sulfide. A solvent may also be present, which may contain polar or nonpolar organic solvents or may be water alone. In other embodiments, the second liquid solution may also contain a nitrogen-containing reagent, such as ammonia or hydrazine. In some embodiments, the pH of the second solution may also be varied.

[0044] A second reagent is selected to react with the adsorbed first reagent to produce a complete monolayer of the artificial SEI compound coated on a substrate. A non-limiting list of the compounds formed includes:

[0045] (a) A x O y Type 2 binary oxide, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, and x and y are stoichiometric coefficients;

[0046] (b) A x By O z Type ternary oxides, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, and x, y and z are stoichiometric coefficients;

[0047] (c) A w B x C y O z A type quaternary oxide, wherein A, B, and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals, or metalloids, and w, x, y, and z are stoichiometric coefficients;

[0048] (d) A x B y Type II halide, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, B is a halogen, and x and y are stoichiometric coefficients;

[0049] (e) A x B y C z Type ternary halide, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, C is a halogen, and x, y and z are stoichiometric coefficients;

[0050] (f) A w B x C y D z A type quaternary halide, wherein A, B, and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals, or metalloids, D is a halogen, and w, x, y, and z are stoichiometric coefficients;

[0051] (g) A x N y Type II nitride, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, and x and y are stoichiometric coefficients;

[0052] (h) A x B y N z Type ternary nitrides, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, and x, y and z are stoichiometric coefficients;

[0053] (i) A w B x C y N z A type quaternary nitride, wherein A, B and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, and w, x, y and z are stoichiometric coefficients;

[0054] (j) A x B y Type II chalcogenides, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, B is a chalcogenide, and x and y are stoichiometric coefficients;

[0055] (k) A x B y C z A type of ternary chalcogenide, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, C is a chalcogenide, and x, y and z are stoichiometric coefficients;

[0056] (l) A w B x C y D z A type quaternary chalcogenide, wherein A, B and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, D is a chalcogenide, and w, x, y and z are stoichiometric coefficients.

[0057] (m) A x C y Type II binary carbides, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, and x and y are stoichiometric coefficients;

[0058] (n) A x B y O z Type II halide oxides, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, B is a halogen, and x, y and z are stoichiometric coefficients;

[0059] (o) A x As y Type II arsenide, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, and x and y are stoichiometric coefficients;

[0060] (p) A x B y As z Type ternary arsenide, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, and x, y and z are stoichiometric coefficients;

[0061] (q) A w B x C y As zA type quaternary arsenide, wherein A, B, and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals, or metalloids, and w, x, y, and z are stoichiometric coefficients;

[0062] (r) A x (PO4) y Type diphosphate, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, and x and y are stoichiometric coefficients;

[0063] (s) A x B y (PO4) z Type III triphosphates, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals, or metalloids, and x, y, and z are stoichiometric coefficients; and

[0064] (t) A w B x C y (PO4) z A type tetraphosphate, wherein A, B, and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals, or metalloids, and w, x, y, and z are stoichiometric coefficients.

[0065] In reactions involving nonionic precursors (e.g., organometallic compounds) and oxidants, such as in the hydrolysis of trimethylaluminum, the organic portion is removed and replaced by metal-oxygen-metal bonds until all bonds are fully saturated. In reactions involving two ionic solutions, such as in the hydrolysis of Cd... 2+ and S 2- In reactions between solutions of ions, the high solubility product constant of the reaction promotes the precipitation of ionic compounds (in this case, CdS), where the substrate promotes the formation of heterogeneous films by minimizing surface energy.

[0066] As discussed above regarding step (a), a continuous substrate coated with a film containing the artificial SEI from step (b) can undergo optional rinsing and filtration steps.

[0067] Steps (a) and (b) can be repeated to form a film containing an artificial SEI of the desired thickness. In some embodiments, the film thickness is from about 0.5 nm to 100 µm.

[0068] In other embodiments, a system is provided for performing the liquid phase deposition method as described above. This system includes a transfer device for transferring a continuous substrate from a first reaction chamber to a second reaction chamber. Therefore, a system is provided that includes a transfer device for transferring a continuous substrate to:

[0069] (a) A first reaction chamber, wherein a continuous substrate is exposed to a first liquid solution containing at least a first reagent to produce a layer containing an adsorbed first reagent on the continuous substrate; and

[0070] (b) A second reaction chamber in which a continuous substrate having a layer containing an adsorbed first reagent is exposed to a second liquid solution containing at least a second reagent, wherein the at least second reagent reacts with the first adsorbed reagent to produce a film containing an artificial SEI coated onto the continuous substrate.

[0071] An automated conveyor system may include a series of rollers, such as tension rollers, positioned to guide or direct a continuous substrate into and out of the first and second reaction chambers. This system can provide a continuous liquid deposition method for coating a film containing an artificial SEI onto the surface of a continuous substrate. The series of rollers is driven by a conveyor motor.

[0072] In some embodiments, the first and second reaction chambers may include sensors for determining or measuring the amount of a first or second liquid solution in the respective reaction chamber or the precursor concentration in each respective reaction chamber. Additionally, the first and second reaction chambers may also include regulating valves electrically driven by the sensors. When the sensor (e.g., a float switch) determines that the liquid solution level is too low, the valve opens, allowing more liquid solution to flow into the reaction chamber from another source. When the sensor determines that the liquid solution is at a desired level, the valve closes, preventing excess liquid solution from flowing into the reaction chamber. In some cases, if the sensor determines that the liquid solution level in the reaction chamber is too high, the valve opens, allowing excess liquid to flow out of the reaction chamber. When the sensor detects a precursor concentration, the valve can expose the tank to a reserve solution with a high precursor concentration if a low precursor solution concentration is detected, and vice versa. An example of such a sensor is an ion-selective electrode.

[0073] In a further embodiment, the system includes a first rinsing chamber located between the first and second reaction chambers. The first rinsing chamber contains a first rinsing solution comprising a first solvent for rinsing a continuous substrate conveyed to the first rinsing chamber by a conveying device to produce a saturated first layer on the continuous substrate, and a first residual solution comprising the first solvent and unreacted first reagent.

[0074] Similarly, the system may also include a second rinsing chamber located after the second reaction chamber. The second rinsing chamber contains a second rinsing solution containing a second solvent for rinsing the continuous substrate conveyed to the second rinsing chamber by the conveying device to produce a film containing an artificial SEI coated onto the continuous substrate.

[0075] Similar to the method described above, in a further embodiment, the system may also include a filtration device for separating unreacted reagents from the solvent in the first and second wash solutions. The filtration device can be any instrument capable of performing such a separation. Preferably, the filtration device is selected from one of the following: a membrane, a filter column or chromatographic column, a chemical or electrochemical separation tank, or an adsorption column.

[0076] While some embodiments described above relate to methods and systems for coating thin films containing artificial SEIs onto continuous substrates using liquid phase deposition, other embodiments of this disclosure are applicable to discrete substrates. Therefore, in some embodiments, a method is provided for coating a thin film containing an artificial SEI layer onto the surface of a discrete substrate, the method comprising:

[0077] (a) A discrete substrate is conveyed to a first reaction chamber containing at least a first liquid solution, the first liquid solution containing a first reagent;

[0078] (b) Expose the discrete substrate from step (a) to a first liquid solution to produce a layer containing an adsorbed first reagent on the surface of the discrete substrate;

[0079] (c) The discrete substrate from step (b) is transferred to a second reaction chamber containing a second liquid solution, the second liquid solution containing at least a second reagent; and

[0080] (d) Exposing the discrete substrate from step (c) to a second liquid solution, wherein at least the second reagent reacts with the first adsorbed reagent to produce a film containing an artificial SEI coated onto the surface of a continuous substrate, the artificial SEI comprising a compound generated by the reaction of the second reagent and the adsorbed first reagent.

[0081] In some embodiments, the discrete substrate is a freestanding sintered pellet or plate of a solid electrolyte, comprising one of the following materials: Li w La x M y O 12 (where M is Nb, Ta, or Zr), Li x MP y S z (where M is Ge or Sn), Li w Al x M y (PO4)3 (where M is Ge or Ti), Li x Ti y M z (PO4)3 (where M is Al, Cr, Ga, Fe, Sc, In, Lu, Y, or La) or Na x Zr2Si y PO12 In all cases, x, y, and z represent stoichiometric coefficients.

[0082] Steps (a) and (b) are performed by conveying a discrete substrate to first and second reaction chambers using a conveying device. Therefore, in another embodiment, this disclosure provides a system for coating a thin film comprising an artificial SEI onto the surface of a discrete substrate, the system comprising:

[0083] A conveying device, the conveying device being used to convey discrete substrates to:

[0084] (a) A first reaction chamber, wherein a discrete substrate is exposed to a first liquid solution containing at least a first reagent to produce a layer containing an adsorbed first reagent on the surface of the discrete substrate; and

[0085] (b) A second reaction chamber in which a discrete substrate having a layer containing an adsorbed first reagent is exposed to a second liquid solution containing at least a second reagent, wherein the at least second reagent reacts with the first adsorbed reagent to produce a monolayer film containing an artificial SEI coated onto the surface of the discrete substrate.

[0086] Compared to the conveying equipment described for continuous substrates, the conveying equipment used in the aforementioned embodiments is improved to accommodate the processing of discrete substrates. In this embodiment, the conveying equipment is a track-based conveying equipment comprising:

[0087] (a) A horizontal track, which is located above the first and second reaction chambers and spans the length of the first and second reaction chambers; and

[0088] (b) A vertical track attached to the horizontal track, the vertical track comprising an arm member driven by an arm motor configured to extend and retract in a substantially vertical direction and to be movable along the horizontal track in a substantially horizontal direction.

[0089] The discrete substrate is connected to a vertical track, which allows the discrete substrate to be transported to the first and second reaction chambers.

[0090] Similarly, steps (a) and (b) can be repeated to form a film containing an artificial SEI of the desired thickness. In some embodiments, the film thickness is from about 0.5 nm to 100 µm.

[0091] As discussed above for continuous substrates, discrete substrates can undergo optional rinsing and filtration steps.

[0092] In an alternative implementation, instead of exposing continuous or discrete substrates to different reaction chambers via a conveying device as discussed above, the continuous or discrete substrates can be placed in a single reaction chamber via a conveying device or otherwise, where they are sequentially exposed to different liquid reaction solutions. For example, a first liquid solution containing a first reagent is introduced into the reaction chamber along with the substrate, wherein the first reagent reacts with the substrate for a certain residence time to produce a layer containing the adsorbed first reagent on the surface of the substrate. Then, as in a plug flow reactor, the first liquid solution is completely removed from the reaction chamber by, for example, evacuation. Next, a second liquid solution containing a second reagent is introduced into the reaction chamber, wherein the second reagent reacts with the first adsorbed reagent to produce a monolayer film containing an artificial SEI coated onto the surface of the substrate. The second liquid solution and the substrate are then removed from the reaction chamber.

[0093] In alternative embodiments, instead of sequentially exposing the substrate to different reaction solutions, multiple reaction solutions or reagents can be simultaneously introduced into a reaction chamber containing the substrate. In these cases, the different reaction solutions or reagents react upon mixing, and a film containing an artificial SEI is deposited on the surface of the substrate immersed in the mixture of reaction solutions or reagents.

[0094] In some aspects, this disclosure provides a method for depositing a thin film comprising an artificial SEI on the surface of a discrete substrate, the method comprising: providing a discrete substrate to a transport device; transferring the discrete substrate via the transport device to a first reaction chamber containing a first liquid solution, the first liquid solution containing at least a first reagent; exposing the discrete substrate to the first liquid solution in the first reaction chamber via the transport device to produce a layer partially coated with at least the first reagent by chemical bonding to the surface of the substrate; rinsing the layer in the first reaction chamber with a first rinsing solution containing a first solvent to remove unreacted first reagent; transferring the substrate from (d) to a second reaction chamber containing a second liquid solution via the transport device, the second liquid solution containing at least a second reagent; exposing the discrete substrate to the second liquid solution in the second reaction chamber via the transport device, wherein the at least second reagent reacts with the at least first reagent by chemical bonding to the surface of the discrete substrate to produce an artificial SEI coating comprising a monolayer on the surface of the discrete substrate, the monolayer comprising a compound generated by the reaction of the at least second reagent with the first reagent; and rinsing the coating in the second reaction chamber with a second rinsing solution containing a second solvent to remove unreacted second reagent.

[0095] In some aspects, this disclosure provides a method for depositing an artificial solid electrolyte interface (SEI) on the surface of a solid electrolyte or solid electrolyte-electrode composite matrix (“substrate”), the method comprising: providing the substrate to a transport device; transferring the substrate via the transport device to a first reaction chamber containing a first liquid solution, the first liquid solution comprising at least a first reagent; exposing the substrate to the first liquid solution in the first reaction chamber via the transport device to produce an artificial SEI layer partially coated with at least the first reagent by chemical bonding to the surface of the substrate; rinsing the layer in the first reaction chamber with a first rinsing solution comprising a first solvent to remove unreacted first reagent; transferring the substrate from (d) to a second reaction chamber containing a second liquid solution, the second liquid solution comprising at least a second reagent; exposing the substrate to the second liquid solution in the second reaction chamber via the transport device, wherein at least the second reagent reacts with at least the first reagent by chemical bonding to the surface of the substrate to produce an artificial SEI coating comprising a monolayer on the surface of the substrate, the monolayer comprising a compound generated by the reaction of at least the second reagent with the first reagent; and rinsing the coating in the second reaction chamber with a second rinsing solution comprising a second solvent to remove unreacted second reagent.

[0096] In some aspects, this disclosure provides a liquid-phase deposition method for generating an artificial solid electrolyte interface (SEI) on the surface of an active material within a porous pre-formed lithium-ion battery pack electrode (e.g., a cathode or anode), the method comprising: providing a porous pre-formed lithium-ion battery pack electrode containing active material to a transport device; transferring the porous pre-formed lithium-ion battery pack electrode via the transport device to a first reaction chamber containing a first liquid solution, the first liquid solution containing at least a first reagent; exposing the porous pre-formed lithium-ion battery pack electrode to the first liquid solution in the first reaction chamber via the transport device to generate a layer of artificial SEI at least partially coated with the first reagent on the surface of the active material within the porous pre-formed lithium-ion battery pack electrode by chemical bonding; and rinsing the partially coated layer in the first reaction chamber with a first rinsing solution containing a first solvent. The process involves: forming an artificial SEI layer on a cloth to remove any unreacted first reagent; transferring the porous preformed lithium-ion battery electrode from (d) to a second reaction chamber containing a second liquid solution, the second liquid solution containing at least a second reagent; exposing the porous preformed lithium-ion battery electrode to the second liquid solution in the second reaction chamber via a transfer device, wherein at least the second reagent reacts with at least the first reagent chemically bonded to the surface of the active material to produce an artificial SEI comprising a monolayer on the surface of the active material within the porous preformed electrode, wherein the artificial SEI does not contribute to interparticle resistance, and wherein said monolayer comprises a compound generated by the reaction of at least the second reagent with the first reagent; and rinsing the artificial SEI in the second reaction chamber with a second rinsing solution containing a second solvent to remove any unreacted second reagent.

[0097] In some aspects, this disclosure provides a battery pack comprising an anode; a cathode; a solid electrolyte or solid electrolyte-electrode composite matrix disposed between the anode and the cathode, wherein the solid electrolyte or the solid electrolyte-electrode composite matrix comprises an artificial solid electrolyte interface (SEI) layer produced by the liquid phase deposition method described herein; and a housing containing the anode, the cathode, the electrolyte, and a polymer separator, wherein the housing provides electrical contact with the anode and the cathode. In some aspects, this disclosure provides a battery pack comprising an anode; a cathode; a solid electrolyte or solid electrolyte-electrode composite matrix disposed between the anode and the cathode; and a housing containing the anode, the cathode, the electrolyte, and a polymer separator, wherein the housing provides electrical contact with the anode and the cathode, wherein at least one of the anode or cathode comprises an artificial solid electrolyte interface (SEI) layer produced by the liquid phase deposition method described herein. In some embodiments, the battery pack further comprises a separator located between the anode and the cathode. Attached Figure Description

[0098] Figure 1 This is a general flow chart of an embodiment of the solution phase deposition method according to the present disclosure. The method includes a rinsing / washing step and a filtration step.

[0099] Figure 2 This is a schematic diagram of one embodiment of a system for coating a thin film containing an artificial SEI layer onto the surface of a battery pack substrate according to the present disclosure.

[0100] Figure 3 This is a description of a thin film comprising an artificial SEI layer according to the present disclosure coated onto the surface of a substrate.

[0101] Figure 4 According to the description of the battery pack in this disclosure, the battery pack consists of an anode and a cathode, and a solid electrolyte present between the anode and the cathode.

[0102] Figure 5 This is based on the description of the solid electrolyte-electrode composite matrix coated with an artificial SEI layer according to this disclosure. Detailed Implementation

[0103] This document provides methods, systems, and compositions for solution-phase deposition of thin films comprising one or more artificial solid electrolyte interface (SEI) layers on the surface of a substrate. To date, techniques for forming conformal coatings (<10 micrometer (μm) thick) on substrates having microstructures with high porosity, tortuosity, and / or a large number of high aspect ratio features (i.e., “non-planar” microstructures) have been ineffective (due to the “line-of-sight” limitation of physical vapor deposition) or expensive and time-consuming, such as those used in conventional atomic layer deposition (ALD). The methods disclosed herein provide a cost-effective means of forming uniform conformal layers on non-planar microstructures.

[0104] The methods and systems described herein are particularly applicable to solid-state electrolytes (SSEs) or solid-state electrolyte-electrode composite matrix substrates. Solid-state electrolyte-electrode composite matrices are typically formed by first mixing solid electrolyte powder with electrode powder in appropriate ratios, adding solvents and / or other necessary additives to produce a slurry, and then casting the slurry onto a current collector. The ratio of solid electrolyte to electrode component powders is precisely adjusted to create physical bonds between electrode powders and between electrolytes throughout the resulting matrix. Examples of SSEs disclosed herein include, but are not limited to, all-solid-state electrolytes, such as inorganic solid electrolytes, solid polymer electrolytes, and composite polymer electrolytes. Figure 5The image shows an example of an embodiment of a solid electrolyte-electrode composite matrix coated with an artificial SEI layer according to the present disclosure. The coated solid electrolyte-electrode composite matrix 500 comprises electrode component powder 502 (gray particles), solid electrolyte powder 504 (white particles), additive 506 (black particles), and an artificial SEI layer 508. Additive 506 may be a conductive additive or a binding additive. Except for the contact points between particles, all particles and surfaces of the matrix 500 are coated with the artificial SEI layer 508, thus not contributing to interparticle resistance. The matrix 500 is layered on a substrate 510.

[0105] The SSE or solid electrolyte-electrode composite matrix substrate disclosed herein can be a continuous substrate or a discrete substrate. As used herein, a “continuous substrate” refers to a substrate having an aspect ratio of at least 10:1 between its two largest dimensions and being sufficiently flexible to be wound onto itself in a roll. It can be made of various materials, including but not limited to metals such as copper, aluminum, or stainless steel, or organic materials such as polyimide, polyethylene, polyetheretherketone (PEEK), polyester, or polyethylene naphthalate (PEN). As used herein, a “discrete substrate” refers to a substrate having an aspect ratio of <10:1 between its two largest dimensions and / or having a length dimension of at least 100 mm and being sufficiently rigid to require handling as a discrete unit.

[0106] The thin film disclosed herein comprises an artificial SEI layer formed during a solution phase deposition method by a reaction of two or more reagents. The artificial SEI layer serves as a protective coating on the constituent particles of a substrate, while allowing the particles to maintain interparticle connectivity. Therefore, the methods described herein can be used to coat the surfaces of components of electrochemical instruments, such as battery packs. In particular, applications that can benefit from the coatings described herein for battery packs, such as lithium-ion battery packs, may include high-voltage cathodes, fast-charging, silicon-containing anodes, less expensive electrolytes, and nanostructured substrates. Thus, in some embodiments, a thin film containing an artificial SEI can be coated onto a battery pack substrate. In some embodiments, the battery pack substrate may be a composite of electrode and solid electrolyte materials. In some embodiments, the electrode may be an anode or cathode. In some embodiments, the battery pack substrate may be a freestanding membrane of a solid electrolyte.

[0107] exist Figure 4The diagram illustrates an embodiment of a battery pack comprising an artificial SEI layer formed by a solution phase deposition method according to the present disclosure and applied at the interfaces between the anode and the solid electrolyte and between the cathode and the solid electrolyte. The battery pack 400 includes a housing 402 housing electrodes 404 (anode) and 406 (cathode). Each electrode has electrical contacts 414a-b extending out of the housing 402. A solid electrolyte 408 is located between the two electrodes and optionally separated by a separator 410. Artificial SEI layers 412a-b are coated on the surface of each electrode. In some embodiments, only the anode / solid electrolyte interface has an artificial SEI. In other embodiments, only the cathode / solid electrolyte interface has an artificial SEI. In some embodiments, the artificial SEI is applied to the anode surface prior to battery construction. In some embodiments, the artificial SEI is applied to the cathode surface prior to battery construction. In some embodiments, the artificial SEI is applied to the solid electrolyte surface.

[0108] exist Figure 1 A simplified flowchart of an embodiment of the solution phase deposition method according to this disclosure is shown. Although Figure 1 The embodiments described herein relate to methods for coating thin films onto the surface of a battery pack substrate. This description represents only the components deposited using the methods and systems provided herein and should not be construed as being limited in any way.

[0109] refer to Figure 1 For example, a battery pack substrate may be exposed in 100 to a first liquid solution containing one or more first reagents in a first reaction chamber to produce a layer containing one or more adsorbed first reagents on the surface of the substrate. As described herein, the substrate may include battery pack electrodes, solid electrolytes (e.g., freestanding membranes), or composites of electrode and solid electrolyte materials.

[0110] The first liquid solution contains at least a first reagent. The first reagent can be any compound capable of reacting with the material of the substrate (i.e., the part to be coated) to form a self-confining layer. In some embodiments, the first reagent is an organometallic compound. Examples of such organometallic compounds include, but are not limited to, aluminum trisec-butoxide, titanium ethoxide, niobium ethoxide, trimethylaluminum, and zirconium tert-butoxide. In another embodiment, the first reagent comprises an aqueous solution containing an ionic compound. Examples include, but are not limited to, zinc acetate, cadmium chloride, zinc chloride, zirconium chloride, and zinc sulfate. In some embodiments, the pH of the first solution can be varied. In some embodiments, the first liquid solution can be a solution comprising both a cation and anion precursor that react to form a solid film; in this case, film growth is limited by film-forming reaction kinetics. In some embodiments, the first liquid solution can be a solution comprising both an organometallic compound and an oxidizing precursor that react to form a solid film; in this case, film growth is limited by film-forming reaction kinetics.

[0111] In embodiments where the first reagent is an organometallic compound, the first liquid solution may further contain a solvent for dissolving or complexing the first reagent. Preferred solvents include organic solvents, such as alcohols (e.g., isopropanol or ethanol), alcohol derivatives (e.g., 2-methoxyethanol), slightly less polar organic solvents (e.g., pyridine or tetrahydrofuran (THF)), or nonpolar organic solvents (e.g., hexane and toluene).

[0112] In one embodiment, the first liquid solution is contained within a first reaction chamber. The reaction chamber must be a sufficiently large instrument to accommodate the receiving substrate and contain the amount of liquid solution used for the reaction to produce the self-confining layer. Such instruments that can be used as reaction chambers include, but are not limited to, tanks, baths, pans, beakers, etc.

[0113] The substrate can be transferred to the first reaction chamber via a conveyor. As described in more detail below, the conveyor can be adapted and positioned in such a way as to guide or direct the substrate in and out of the first chamber.

[0114] In some embodiments, the substrate may be completely or partially immersed in the first and second liquid solutions in the first and second reaction chambers, respectively. In other embodiments, the substrate may be sprayed with the first and second liquid solutions in the first and second reaction chambers, respectively.

[0115] In another embodiment, the substrate can be conveyed below the slit-die coater, from which a first liquid solution is continuously dispensed to produce a two-dimensional liquid film. The substrate conveying speed and the fluid flow rate through the die determine the thickness of the liquid film. The solvent can then simply evaporate to form a solid film of dissolved components, or the liquid film can react to precipitate a thin film containing an artificial SEI on the substrate surface. The resulting solid film can be as thin as an atomic monolayer or as thick as 100 micrometers. The reaction can take place while the solvent is still present or after the solvent has evaporated. If residual solvent remains until after the coating process is complete, it can be removed using various techniques, such as blade scraping, air knife, metering knife, or similar techniques. The entire slit-die coating process can then be repeated to produce a new film with a different chemical composition or simply a thicker coating with the same chemical composition. In this case, the reaction chamber simply encompasses the area where the slit-die coater is located and does not necessarily resemble the enclosed space implied by the term "chamber."

[0116] In another embodiment, the substrate can be conveyed through a tank containing a coating solution and a gravure roller. In this embodiment, the gravure roller continuously transfers fluid from the immersion tank to the adjacent substrate due to the preferential surface tension (wetting) of the coating solution on the substrate and roller. As in slot die coating, the result is initially a two-dimensional liquid film on the substrate surface. For example, the specific composition of the solution, substrate, and roller may affect the surface tension of the fluid on both the substrate and the roller, thus affecting the coating efficiency of the method. The solvent can then simply evaporate to form a solid film of dissolved components, or the liquid film may react to precipitate a film containing an artificial SEI on the substrate surface. The resulting solid film can be as thin as an atomic monolayer or as thick as 100 micrometers. The reaction can take place while the solvent is still present or after the solvent has evaporated. If residual solvent remains until after the coating process is complete, it can be removed by various techniques, such as blade scraping, air knife, metering knife, or similar techniques. The entire gravure coating method can then be repeated to produce new films with different chemical compositions or simply to produce thicker coatings with the same chemical composition.

[0117] Multiple sequential, repetitive steps of the same method (i.e., slot die or gravure coating) can be performed using the same or different solutions. Solutions can be separated (e.g., in a first solution, a second solution, etc.) to avoid cross-contamination, for example, or to prevent homogeneous nucleation when a heterogeneous film-forming reaction is preferred.

[0118] The substrate is exposed to the first liquid solution for a sufficient period of time (“residence time”) to allow one or more first reagents to adsorb onto the substrate surface and form a continuous layer (i.e., a self-confined layer). Examples of method variables that can affect this step include solution and substrate temperatures, residence time, and reagent concentration.

[0119] The advantages of this method and system are that the solvents used have different specific heat capacities and can also be used as a medium for both heat transfer and precursor transfer, resulting in faster and more efficient substrate heating. Compared to their pure analogues, the precursors dissolved in solution are also much more stable in terms of exposure to air, resulting in improved safety and easier handling.

[0120] Optionally, the substrate may undergo a first rinsing / washing step 102, thereby removing excess first reagent from step 100 with a solvent. Here, most or all of the unadsorbed first reagent is removed from the substrate surface before moving the substrate to the next method step. Key method variables include solvent temperature, substrate temperature, and residence time. 102 in Figure 1 It is shown as a single step; however, in some embodiments, the step may be repeated or may have additional rinsing / washing steps to improve the removal of the first reagent.

[0121] The rinsing step leaves exactly a saturated (i.e., purified) first layer on the substrate and a residual solution in the reaction chamber containing the first solvent, one or more unreacted first reagents, and other reaction byproducts.

[0122] As an optional step, to recover the solvent and any unreacted reagents used in the rinsing step, the residual solution can be passed to filtration step 103. The filtration step separates the solvent from unreacted reagents (and any reaction byproducts). The filtration step also prevents cross-contamination between chambers and avoids slow contamination of the rinsing solution by reagents during operation. A continuous filtration rinsing bath not only maintains the purity of the rinsing solvent but can also be used as a material recovery system, thereby improving the material utilization efficiency of the method. Any filtration technique known in the art can be used. Preferred techniques include, but are not limited to, membrane separation, chemical precipitation, ion exchange, electrochemical removal, physical adsorption, and flow filtration chromatography.

[0123] The separated solvent can be recycled back to rinsing step 102 for reuse. Similarly, the filtered unreacted one or more first reagents can be recycled back to step 100 for further use in the method (not shown).

[0124] Then, in 104, the battery pack substrate having a partially coated layer containing the adsorbed first reagent (i.e., a self-restricting layer) can be exposed to a second liquid solution containing the second reagent in a second reaction chamber.

[0125] In some embodiments, the second liquid solution may contain an oxidizing agent, such as an oxide or sulfide source, examples of which include, but are not limited to, water, thioacetamide, and sodium sulfide. A solvent may also be present, which may contain polar or nonpolar organic solvents or may be water alone. In other embodiments, the second liquid solution may also contain a nitrogen-containing reagent, such as ammonia or hydrazine. In some embodiments, the pH of the second solution may also be varied.

[0126] The second reagent has a different and unique composition compared to the first reagent. The second reagent is selected to react with the adsorbed first reagent to produce a complete monolayer of the artificial SEI compound coated on a substrate.

[0127] In some implementations, the entire membrane can be formed solely from the reagent exposed to the substrate from the first liquid solution. In this case, the second solution can be completely skipped.

[0128] In some embodiments, the formed compound may comprise metal oxides, such as Al₂O₃ and TiO₂. In other embodiments, the formed compound may comprise transition metal dichalcogenides (TMDs). Typical examples of such materials follow the general chemical formula MX₂, where M is a transition metal, such as Mo, W, Ti, etc., and X is S or Se. In some embodiments, the compound consists of any combination of polymers including polyethylene oxide (PEO), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), polydimethylsiloxane (PDMS), and polyvinylpyrrolidone (PVP). When combined with lithium salts (e.g., especially LiClO₄, LiPF₆, or LiNO₃), such polymers can produce solid polymer electrolyte films. In some embodiments, the compound may comprise sulfides or selenides of, for example, Mo, Ti, or W. These materials vary widely in their electronic properties (e.g., band gaps) and can therefore be used to form custom semiconductor heterojunctions, which, for example, would block electron transfer necessary for degradation reactions during the operation of lithium-ion battery packs. Specifically, such a mechanism can be used to block degradation reactions on both the anode and cathode surfaces.

[0129] In some implementation schemes, the resulting compound may be selected from:

[0130] (a) A x O y Type 2 binary oxide, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, and x and y are stoichiometric coefficients;

[0131] (b) A x B y O zType ternary oxides, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, and x, y and z are stoichiometric coefficients;

[0132] (c) A w B x C y O z A type quaternary oxide, wherein A, B, and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals, or metalloids, and w, x, y, and z are stoichiometric coefficients;

[0133] (d) A x B y Type II halide, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, B is a halogen, and x and y are stoichiometric coefficients;

[0134] (e) A x B y C z Type ternary halide, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, C is a halogen, and x, y and z are stoichiometric coefficients;

[0135] (f) A w B x C y D z A type quaternary halide, wherein A, B, and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals, or metalloids, D is a halogen, and w, x, y, and z are stoichiometric coefficients;

[0136] (g) A x N y Type II nitride, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, and x and y are stoichiometric coefficients;

[0137] (h) A x B y N z Type ternary nitrides, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, and x, y and z are stoichiometric coefficients;

[0138] (i) A w B x C y N z A type quaternary nitride, wherein A, B and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, and w, x, y and z are stoichiometric coefficients;

[0139] (j) Ax B y Type II chalcogenides, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, B is a chalcogenide, and x and y are stoichiometric coefficients;

[0140] (k) A x B y C z A type of ternary chalcogenide, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, C is a chalcogenide, and x, y and z are stoichiometric coefficients;

[0141] (l) A w B x C y D z A type quaternary chalcogenide, wherein A, B and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, D is a chalcogenide, and w, x, y and z are stoichiometric coefficients.

[0142] (m) A x C y Type II binary carbides, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, and x and y are stoichiometric coefficients;

[0143] (n) A x B y O z Type II halide oxides, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, B is a halogen, and x, y and z are stoichiometric coefficients;

[0144] (o) A x As y Type II arsenide, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, and x and y are stoichiometric coefficients;

[0145] (p) A x B y As z Type ternary arsenide, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, and x, y and z are stoichiometric coefficients;

[0146] (q) A w B x C y As z A type quaternary arsenide, wherein A, B, and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals, or metalloids, and w, x, y, and z are stoichiometric coefficients;

[0147] (r) A x (PO4) y Type diphosphate, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, and x and y are stoichiometric coefficients;

[0148] (s) A x B y (PO4) z Type III triphosphates, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals, or metalloids, and x, y, and z are stoichiometric coefficients; and

[0149] (t) A w B x C y (PO4) z A type tetraphosphate, wherein A, B, and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals, or metalloids, and w, x, y, and z are stoichiometric coefficients.

[0150] In reactions involving nonionic precursors (e.g., organometallic compounds) and oxidants, such as in the hydrolysis of trimethylaluminum, the organic portion is removed and replaced by metal-oxygen-metal bonds until all bonds are fully saturated. In reactions involving two ionic solutions, such as in the hydrolysis of Cd... 2+ and S 2- In reactions between solutions of ions, the high solubility product constant of the reaction promotes the precipitation of ionic compounds (in this case, CdS), where the substrate promotes the formation of heterogeneous films by minimizing surface energy.

[0151] Similar to step 102, the electrode from step 104 is then directed to a second rinsing / washing step 106 to remove unadsorbed / unreacted second reagent.

[0152] In some embodiments, the thickness of the film containing the artificial SEI can be from about 0.5 nm to 100 µm. For example, the thickness of the film can be in the range of 0.5 nm-10 nm, 10 nm-50 nm, 50 nm-100 nm, 100 nm-500 nm, 500 nm-1 µm, 1 µm-10 µm, 10 µm-50 µm, or 50 µm-100 µm.

[0153] In some embodiments, the process can be repeated 100 to 106 times until an artificial SEI coating of the desired thickness is formed on the substrate. This process is represented by 108, in which the substrate coated with the artificial SEI is guided back to step 100 for further processing (ring formation). In some embodiments, these steps are repeated with different precursors to produce a coating comprising a stack of artificial SEI layers containing various compounds.

[0154] Additionally, during steps 102 and 106, the solvent can be continuously or periodically filtered, rinsed, or washed to separate and recover unreacted one or more reagents from the solvent. This filtration step is indicated in steps 103 and 105, respectively. Both the precursor and the solvent can then potentially be recycled back into the method. Here, solvent recycling is indicated by a return arrow. These filtration steps will save significant material costs over the life of the equipment. A filtration step can be incorporated into the design for each washing and rinsing step. The filtration technique is preferably tailored to the type of reagent used in steps 100 and 104. For example, aqueous ionic solutions may require adequate filtration of the type of filter column used in the deionizer. However, organometallic compounds can be better removed by tangential flow filtration systems, such as those that exclude by molecular weight.

[0155] exist Figure 2 The diagram shows an embodiment of a system for coating a film containing an artificial SEI onto a substrate surface. Figure 2 In this context, the reaction chamber is shown as a tank or bath containing a sequential reaction solution; the substrate is conveyed into the reaction chamber with the aid of a conveying device. Although Figure 2 The embodiments described herein relate to methods for coating a thin film containing an artificial SEI onto the surface of a battery pack substrate. This description represents only the parts coated using the methods and systems provided herein and should not be construed as limiting in any way.

[0156] Figure 2 The conveying equipment is particularly suitable and adapted to guide or direct the battery pack substrate in a sequential manner into and out of the first and second reaction chambers.

[0157] The preferred automated conveying equipment comprises a series of rollers, such as tension rollers, positioned to guide or direct the substrate into and out of the first and second reaction chambers. Thus, the system can provide a continuous liquid deposition method for coating a film containing an artificial SEI onto the surface of a substrate. The series of rollers 202a-i is driven by a conveying motor (not shown). The rollers 202a-i are operated and oriented in such a way that the substrate can be conveyed through the system, as discussed in more detail below. System 200 also includes a series of chambers 205, 207, 215, and 217.

[0158] In some embodiments, the first and second reaction chambers may include sensors for determining or measuring the volume of the first or second liquid solution in the respective reaction chamber or the precursor concentration in each respective reaction chamber. Additionally, the first and second reaction chambers may also include regulating valves electrically driven by the sensors. When the sensor (e.g., a float switch) determines that the liquid solution is too low, the valve opens, allowing more liquid solution to flow into the reaction chamber from another source. In some cases, a pump (e.g., a peristaltic pump) is used to drive the liquid solution into the reaction chamber. When the sensor determines that the liquid solution is at a desired level, the valve closes, preventing excess liquid solution from flowing into the reaction chamber. In some cases, if the sensor determines that the liquid solution in the reaction chamber is too high, the valve opens, allowing excess liquid to flow out of the reaction chamber. In cases where the sensor detects a precursor concentration, the valve can expose the tank to a reserve solution with a high precursor concentration if a low precursor solution concentration is detected, and vice versa. An example of such a sensor is an ion-selective electrode.

[0159] In a further embodiment, the system includes a first rinsing chamber located between the first and second reaction chambers. The first rinsing chamber contains a first rinsing solution comprising a first solvent for rinsing a substrate conveyed to the first rinsing chamber by a conveying device to produce a saturated first layer on the substrate, and a first residual solution comprising the first solvent and unreacted first reagent.

[0160] Similarly, the system may also include a second rinsing chamber located after the second reaction chamber. The second rinsing chamber contains a second rinsing solution containing a second solvent, used to rinse the substrate conveyed to the second rinsing chamber by the conveying equipment to produce a film containing an artificial SEI coated onto the substrate.

[0161] Chamber 205 is a first reaction chamber containing a first liquid solution comprising a first reagent and a solvent.

[0162] Chamber 207 is a first rinsing chamber located after the first reaction chamber 205, containing a first rinsing solution comprising a first solvent. A first filtration device 209 is connected to the first rinsing chamber 207. The first filtration device 209 has a residue tube 213 and a permeate collection tube 211 connected to the first rinsing chamber 207.

[0163] Another chamber 215 is a second reaction chamber located after the first rinsing chamber 207, and contains a second liquid solution comprising a second reagent and a solvent.

[0164] Chamber 217 is a second rinse chamber located after the second rinse chamber 215. The second rinse chamber 217 contains a second rinse solution containing a solvent. A second filter device 219 is connected to the second rinse chamber 217. The second filter device 219 has a residue tube 223 and a permeate collection tube 221 connected to the second rinse chamber 217.

[0165] System 200 further includes valves 225a-d located in each of chambers 205, 207, 215, and 217, respectively. Valves 225a-d are connected to a replenishment source (not shown) that, when needed, provides additional first liquid solution, second liquid solution, first reagent, second reagent, or solvent, as in the case of first chamber 215 and second chamber 215, or additional first or second rinse solution, as in the case of first rinse chamber 207 and second rinse chamber 217. Valves 225a-d may be electrically actuated and opened by triggering a sensor (not shown) adapted to monitor or measure the volume or concentration of the liquid solution in the chamber. The sensor may be immersed in the liquid solution in each chamber.

[0166] In operation, a first portion of substrate 203 is initially placed on a first roller 202a, which is part of the conveyor 201. Typically, the first portion is attached, for example by adhesive or tape, to guide material that passes through the remaining portion of rollers 202b-i. In this way, the guide material can guide the substrate through the conveyor 201 during the process. Once the portion of the substrate placed on roller 202a has been conveyed to roller 202i, or when the coating of the entire substrate is complete, the guide material can then be removed from the substrate. Examples of such guide material can come from previous rolls of substrate. Prior to coating a particular substrate, a previous roll of substrate may have already had a long tail length without active material (only foil). Once the previous roll has been processed, this residue is left on the conveyor, and the active material can be cut and removed. The remaining portion is then used as a guide to guide the next roll of substrate through the conveyor.

[0167] Therefore, a first portion of substrate 203 is also conveyed into the first reaction chamber 205 by the movement of a second roller 202b located within the first reaction chamber 205. The first portion of substrate 203 is exposed to a first liquid solution within the first reaction chamber 205 to produce a self-restricted layer containing an adsorbed first reagent on the surface of the first portion of the substrate. The first portion of substrate 203 remains in the first reaction chamber 205 for a certain period of time to allow the reaction to occur. Once the reaction is substantially complete, the first portion of substrate 203 is removed from the first reaction chamber 205 by moving upwards to a third roller 202c.

[0168] When this occurs, a second portion of substrate 203 is transferred to the first reaction chamber 205. The transfer device operates continuously until the required amount of substrate is coated with a film.

[0169] The first portion returns to the substrate 203 and is then conveyed to the first rinse chamber 207 by the movement of the fourth roller 202d located within the first rinse chamber 207. The first rinse chamber 207 contains a first rinse solution containing a first solvent for rinsing the substrate 203 to produce a saturated first layer on the substrate, and a first residual solution containing the first solvent and unreacted first reagent.

[0170] The system may also include a filtration device for separating unreacted reagents from the solvent in the first and second wash solutions. The filtration device can be any instrument capable of performing such a separation. Preferably, the filtration device is selected from one of the following: membrane, filter column or chromatographic column, chemical or electrochemical separation tank, or adsorption column.

[0171] When needed, the first rinse solution is passed to the first filter device 209 to separate the unreacted first reagent from the first solvent. Compared to the first rinse solution, the first filter device 209 produces a permeate stream rich in unreacted first reagent and lean in first solvent, and a residual stream rich in first solvent and lean in unreacted first reagent. The permeate stream is collected in the permeate collection pipe 211, which can be recycled or sent back to the first reaction chamber 205. The residual stream is recycled back to the first rinse chamber 207 via the residual pipe 213. The filter device 209 can be operated periodically or continuously. From the first rinse chamber 207, the first portion of the substrate 203 is removed from the first rinse chamber 207 by moving upwards to the fifth roller 202e.

[0172] The first portion of the substrate 203 is then conveyed into the second reaction chamber 215 by moving downwards to the sixth roller 202f located within the second reaction chamber 215. The second reaction chamber 215 contains a second liquid solution containing at least a second reagent. Within the second reaction chamber 215, the substrate 203 is exposed to the second liquid solution, which reacts with the first adsorbed reagent to produce a monolayer film containing an artificial SEI coated onto the surface of the substrate. After the reaction is substantially complete, the first portion of the substrate 203 is removed from the second reaction chamber 215 by moving upwards to the seventh roller 202g.

[0173] Next, the first portion of the substrate 203 is also conveyed to the second rinsing chamber 217 by moving downwards to the eighth roller 202h located within the second rinsing chamber 217. The second rinsing chamber 217 contains a second rinsing solution containing a second solvent for rinsing the substrate to produce a purified monolayer artificial SEI coated on the surface of the substrate 203, and a second residual solution containing the second solvent and unreacted second reagent.

[0174] Similar to the first rinse solution, the second rinse solution can be sent to the second filtration device 219. Compared to the second rinse solution, the second filtration device 219 produces a permeate stream rich in unreacted second reagent and lean in second solvent, and a residual stream rich in second solvent and lean in unreacted second reagent. The permeate stream is collected in the permeate collection tube 221 and can be recycled or sent back to the second reaction chamber 215. The residual stream is recycled back to the second rinse chamber 217 via the residual tube 223. The filtration device 219 can be operated periodically or continuously.

[0175] Finally, the first portion of substrate 203 is removed from the second rinsing chamber 217 of the ninth roller 202i, which is being conveyed upwards. From here, the first portion can be collected or rolled up until the remaining desired portion of the substrate is coated with a film containing an artificial SEI.

[0176] and Figure 2 Similar embodiments to those described in this disclosure may include replacing bath-deposition reaction chambers 205 and 215 with a slot die or gravure coating reaction chamber (not shown). In such embodiments, rinsing chambers 207 and 217 may or may not be present, depending on the requirements of the rinsing step. In such embodiments, or even in Figure 2 In the embodiments described herein, excess solution removal techniques (e.g., air knives, scrapers, metering knives, or similar techniques) can be used instead of a rinsing step. In another similar embodiment, 215 may be completely absent, as the entire deposition reaction can take place in 205. Therefore, the apparatus of this disclosure can be considered modular in both its deposition and transport aspects and can be assembled in any particular manner to facilitate a specific solution deposition method.

[0177] exist Figure 3 The image shows an example of an embodiment of a coated battery pack substrate according to the present disclosure. The coated substrate 300 comprises substrate constituent particles (i.e., the active layer) 302 coated with a thin film 303 containing an artificial SEI. The thickness of the artificial SEI-containing thin film 303 can be between 0.5 nm and 100 μm. The substrate constituent particles 302 are located on top of a substrate 301, in this case, which is a foil substrate. The thin film coating covers all particle surfaces except for the contact points between particles, thus not contributing to interparticle resistance. In embodiments where the coated substrate 300 is an electrode, the coated electrode will be located near the solid electrolyte within the battery pack.

[0178] The methods disclosed herein can be implemented using or by means of a computer system. The computer system can be involved in many different aspects of the operation of the method, including, but not limited to, regulating various aspects of the delivery device, such as guiding the movement of the delivery device by moving the part to be coated in and out of the reaction chamber; controlling the opening and closing time of valves; guiding liquids (e.g., reagents and buffer solutions) into the reaction chamber by detecting liquid volume via sensor readings; and regulating pumps. In some aspects, the computer system is implemented to automate the methods and systems disclosed herein.

[0179] The computer system may include or communicate with an electronic display, which contains a user interface (UI) for providing, for example, the analysis results of one or more samples. Examples of UF include, but are not limited to, graphical user interfaces (GUIs) and web-based user interfaces.

[0180] The methods and systems provided above are now further described by way of the following embodiments, which are intended to be illustrative and not to limit the scope or basic principles in any way. Example

[0181] Example 1: Deposition of TiO2

[0182] First, titanium isopropoxide is dissolved in a suitable anhydrous solvent (e.g., dry isopropanol) and adsorbed onto the surface of a substrate. Then, excess unadsorbed titanium isopropoxide is removed from the part to be coated (e.g., an electrolyte or electrolyte-electrode complex) using a rinsing solvent. Next, the substrate is introduced into a solution of an oxidant (e.g., water) dissolved in a suitable solvent (e.g., isopropanol). Hydrolysis results in the loss of alkoxide ligands to 2-propanol, leaving the adsorbed portion with added hydroxyl groups. In a further step, excess water and solvent are removed from the solution by rinsing solvent. A single monolayer of titanium oxide is produced. This process can be repeated to produce increased thickness.

[0183] Example 2: Deposition of CdS

[0184] Cadmium sulfate (CdSO4) first dissolves in an aqueous solution, producing Cd adsorbed on the substrate surface. 2+ Ions. Remove excess unadsorbed Cd from the substrate. 2+ The substrate is then introduced into an aqueous solution containing anionic sulfur precursors (e.g., thiourea or Na₂S). The pH of the precursor solution can be varied to control the reaction rate. The high solubility product constant of CdS in this reaction results in the precipitation of a single monolayer of CdS on the substrate surface, where surface energy is minimized to promote nucleation.

[0185] Example 3: Deposition of TiN

[0186] Immerse or expose the substrate (or other part to be coated) in an anhydrous ethanol solution of dissolved titanium ethoxide. Remove excess precursor from the substrate. Expose the substrate to a solution containing a nitrogen precursor, such as ammonia in pyridine or hydrazine in THF. The reaction of the precursor with adsorbed titanium ethoxide produces a single monolayer of TiN.

[0187] It should be understood from the foregoing that, although specific embodiments have been described and illustrated, various modifications are possible and contemplated herein. This disclosure is also not intended to be limited by the specific examples provided in the specification. While certain embodiments have been described with reference to the foregoing specification, the description and illustration of preferred embodiments herein are not intended to be construed as limiting. Furthermore, it should be understood that all aspects of this disclosure are not limited to the specific descriptions, configurations, or relative proportions presented herein, and depend on a variety of conditions and variables. Various modifications in form and detail of the embodiments will be apparent to those skilled in the art. Therefore, this disclosure is also intended to cover any such modifications, variations, and equivalents.

Claims

1. A method for depositing a thin film comprising an artificial solid electrolyte interface (SEI) on the surface of a solid electrolyte or a solid electrolyte-electrode composite matrix, the method comprising: a) Providing the solid electrolyte or solid electrolyte-electrode composite matrix to a track transport device, wherein the solid electrolyte or solid electrolyte-electrode composite matrix is ​​formed as a discrete substrate; b) Transferring the solid electrolyte or solid electrolyte-electrode composite matrix to a first reaction chamber containing a first liquid solution via the conveying device, wherein the first liquid solution contains at least a first reagent; c) Exposing the solid electrolyte or solid electrolyte-electrode composite matrix to the first liquid solution in the first reaction chamber via the conveying device to produce a layer coated with the at least first reagent portion chemically bonded to the surface of the solid electrolyte or solid electrolyte-electrode composite matrix; d) Rinse the layer in the first reaction chamber with a first rinsing solution containing a first solvent to remove unreacted first reagent; e) Transfer the solid electrolyte or solid electrolyte-electrode composite matrix from (d) to a second reaction chamber containing a second liquid solution via the conveying device, the second liquid solution containing at least a second reagent; f) Exposing the solid electrolyte or solid electrolyte-electrode composite matrix to the second liquid solution in the second reaction chamber via the conveying device, wherein the at least second reagent reacts with the at least first reagent chemically bonded to the surface of the substrate to produce the artificial solid electrolyte interface comprising a monolayer on the surface of the solid electrolyte or solid electrolyte-electrode composite matrix, the monolayer comprising a compound generated by the reaction of the first reagent with the at least second reagent; and g) Rinse the monolayer in the second reaction chamber with a second rinsing solution containing a second solvent to remove unreacted second reagent; The track conveying device includes a horizontal track located above the first and second reaction chambers and a vertical track attached to the horizontal track. The vertical track includes an arm member that extends and retracts in a substantially vertical direction and is movable along the horizontal track in a substantially horizontal direction.

2. The method of claim 1, wherein the thickness of the thin film coating of the artificial solid electrolyte interface is from 0.5 nm to 100 µm.

3. The method of any one of claims 1-2, wherein the thickness of the solid electrolyte or solid electrolyte-electrode composite matrix in (a) is from 10 nm to 1,000 µm.

4. The method of any one of claims 1-2, wherein the solid electrolyte or solid electrolyte-electrode composite matrix in (a) has pores ranging in size from 0.1 nm to 100 µm.

5. The method according to any one of claims 1-2, wherein the porosity of the solid electrolyte or solid electrolyte-electrode composite matrix in (a) is 1-99%.

6. The method of any one of claims 1-2, wherein the solid electrolyte or solid electrolyte-electrode composite matrix in (a) is a continuous substrate having an aspect ratio greater than 10:1 between its maximum dimensions.

7. The method of any one of claims 1-2, wherein the solid electrolyte or solid electrolyte-electrode composite matrix in (a) is a discrete substrate having a length dimension of at least 100 mm and sufficient rigidity to be processed as a discrete unit.

8. The method of claim 6, wherein the solid electrolyte or solid electrolyte-electrode composite matrix is ​​composed of a flexible foil current collector coated with a composite matrix of solid electrolyte and electrode material.

9. The method of claim 8, wherein the foil current collector comprises metal.

10. The method of claim 9, wherein the metal is Cu, Al, or stainless steel.

11. The method of claim 6, wherein the solid electrolyte or solid electrolyte-electrode composite matrix is ​​a solid polymer-electrolyte membrane.

12. The method of claim 8, wherein the electrode material within the composite matrix of the solid electrolyte and the electrode material comprises one or more of the following: graphite, Si, Sn, Ge, Al, P, Zn, Ga, As, Cd, In, Sb, Pb, Bi, SiO, SnO2, Si, Sn, lithium metal, LiNi x Mn y Co z O2, LiNi x Co y Al z O2, LiMn x Ni y O z LiMnO2, LiFePO4, LiMnPO4, LiNiPO4, LiCoPO4, LiV2O5, sulfur or LiCoO2, where x, y and z are stoichiometric coefficients.

13. The method of claim 8, wherein the solid electrolyte within the composite matrix of the solid electrolyte and the electrode material comprises one or more of the following: Li w La x M y O 12 (where M is Nb, Ta, or Zr), Li x MP y S z (where M is Ge or Sn), Li w Al x M y (PO4)3 (where M is Ge or Ti), Li x Ti y M z (PO4)3 (where M is Cr, Ga, Fe, Sc, In, Lu, Y, or La) or Na x Zr2Si y PO 12 In all cases, x, y, and z represent stoichiometric coefficients.

14. The method of claim 11, wherein the solid polymer-electrolyte comprises one or more of the following polymers: Polyethylene oxide (PEO), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), polydimethylsiloxane (PDMS), and polyvinylpyrrolidone (PVP), when combined with lithium salts, can form solid polymer electrolyte films.

15. The method of claim 14, wherein the lithium salt is selected from LiClO4, LiPF6 or LiNO3.

16. The method of claim 8, wherein the electrode material is composed of an active material.

17. The method of any one of claims 1-2, wherein the conveying device comprises a series of rollers or tracks for transferring the solid electrolyte or solid electrolyte-electrode composite matrix to the first reaction chamber and / or the second reaction chamber in (b) and (e).

18. The method of any one of claims 1-2, wherein the solid electrolyte or solid electrolyte-electrode composite matrix of (c) and (f) is exposed to the first and second liquid solutions by means of immersion, spraying, slot die coating, bath coating or gravure roller coating.

19. The method of any one of claims 1-2, further comprising: The first residual solution containing the first solvent and the unreacted first reagent is passed through a first filtration step to separate the unreacted first reagent from the first solvent; and A second residual solution containing the second solvent and the unreacted second reagent is passed through a second filtration step to separate the unreacted second reagent from the second solvent.

20. The method of any one of claims 1-2, further comprising: The recovered unreacted first or second reagent is recycled back into the first or second liquid solution, respectively. and The recovered first or second solvent is recycled back to the first or second rinsing solution, respectively.

21. The method of claim 19, wherein the first and second filtration steps are performed using membrane separation, chemical precipitation, ion exchange, electrochemical removal, physical adsorption, flow filtration chromatography, or any combination thereof.

22. The method of any one of claims 1-2, wherein the first liquid solution and the second liquid solution comprise more than one reagent.

23. The method of any one of claims 1-2, wherein (a)-(g) are repeated to produce the continuous growth of a plurality of stacked monolayers, thereby producing a thin film coating comprising one or more artificial solid electrolyte interface layers with a total thickness between 0.5 nanometers (nm) and 100 micrometers (µm).

24. The method of any one of claims 1-2, wherein the compound produced is selected from one of the following: a)A x O y Type 2 binary oxide, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, and x and y are stoichiometric coefficients; b)A x B y O z Type ternary oxides, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, and x, y and z are stoichiometric coefficients; c)A w B x C y O z A type quaternary oxide, wherein A, B, and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals, or metalloids, and w, x, y, and z are stoichiometric coefficients; d)A x B y Type II halide, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, B is a halogen, and x and y are stoichiometric coefficients; e)A x B y C z Type ternary halide, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, C is a halogen, and x, y and z are stoichiometric coefficients; f)A w B x C y D z A type quaternary halide, wherein A, B, and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals, or metalloids, D is a halogen, and w, x, y, and z are stoichiometric coefficients; g)A x N y Type II nitride, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, and x and y are stoichiometric coefficients; h)A x B y N z Type ternary nitrides, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, and x, y and z are stoichiometric coefficients; i)A w B x C y N z A type quaternary nitride, wherein A, B and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, and w, x, y and z are stoichiometric coefficients; j)A x B y Type II chalcogenides, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, B is a chalcogenide, and x and y are stoichiometric coefficients; k)A x B y C z A type of ternary chalcogenide, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, C is a chalcogenide, and x, y and z are stoichiometric coefficients; l)A w B x C y D z A type quaternary chalcogenide, wherein A, B and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, D is a chalcogenide, and w, x, y and z are stoichiometric coefficients. m)A x C y Type II binary carbides, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, and x and y are stoichiometric coefficients; n)A x B y O z Type II halide oxides, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, B is a halogen, and x, y and z are stoichiometric coefficients; o)A x As y Type II arsenide, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, and x and y are stoichiometric coefficients; p)A x B y As z Type ternary arsenide, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals or metalloids, and x, y and z are stoichiometric coefficients; q)A w B x C y As z A type quaternary arsenide, wherein A, B, and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals, or metalloids, and w, x, y, and z are stoichiometric coefficients; r)A x (PO4) y Type diphosphate, wherein A is an alkali metal, alkaline earth metal, transition metal, half-metal or metalloid, and x and y are stoichiometric coefficients; s)A x B y (PO4) z Type III triphosphates, wherein A and B are any combination of alkali metals, alkaline earth metals, transition metals, half-metals, or metalloids, and x, y, and z are stoichiometric coefficients; and t)A w B x C y (PO4) z A type tetraphosphate, wherein A, B, and C are any combination of alkali metals, alkaline earth metals, transition metals, half-metals, or metalloids, and w, x, y, and z are stoichiometric coefficients.

25. The method of claim 23, wherein the film comprising the artificial solid electrolyte interface, generated from the monolayer or stacked monolayers, is composed of at least one or more metalcone polymers.

26. The method of claim 25, wherein the one or more metalcones are produced by a reaction between a first reagent comprising an organometallic compound and a second reagent comprising an organic molecule.

27. The method of claim 26, wherein the first reagent is an organometallic compound comprising an organic portion and a metal comprising Al, Zn, Si, Ti, Zr, Hf, Mn and / or V, and the second reagent is an organic molecule comprising ethylene glycol, glycerol, erythritol, xylitol, sorbitol, mannitol, butylene glycol, pentanediol, hydroquinone, hexanediol, lactic acid, triethanolamine, p-phenylenediamine, glycidyl ether, caprolactone, fumaric acid, aminophenol and / or diaminodiphenyl ether.

28. The method of claim 23, wherein the film comprising the artificial solid electrolyte interface generated from the monolayer or stacked monolayers is composed of at least one or more polymers comprising polyamide, polyimide, polyurea, polyoxymethylene, fluorinated elastomer or any combination thereof.

29. The method of any one of claims 1-2, wherein the first and second reaction chambers are in the form of a tank, a tray, or a bath.

30. The method of any one of claims 1-2, wherein the first and second reaction chambers include sensors for determining the amount of the first or second liquid solution in the respective reaction chambers.

31. The method of claim 30, wherein the first and second reaction chambers include valves for adjusting the amount of a first or second liquid solution in their respective reaction chambers, the valves being controlled by the sensor in each reaction chamber.

32. The method of claim 7, wherein the solid electrolyte or the solid electrolyte within the solid electrolyte-electrode composite matrix comprises one or more of the following: Li w La x M y O 12 (where M is Nb, Ta, or Zr), Li x MP y S z (where M is Ge or Sn), Li w Al x M y (PO4)3 (where M is Ge or Ti), Li x Ti y M z (PO4)3 (where M is Al, Cr, Ga, Fe, Sc, In, Lu, Y, or La) or Na x Zr2Si y PO 12 In all cases, x, y, and z represent stoichiometric coefficients.

33. A method for depositing an artificial solid electrolyte interface (SEI) on the surface of a discrete substrate, the method comprising: a) Providing the discrete substrate onto a track conveying device; b) Transferring the discrete substrate to a first reaction chamber containing a first liquid solution via the conveying device, the first liquid solution containing at least a first reagent; c) Exposing the discrete substrate to the first liquid solution in the first reaction chamber via the conveying device to produce a layer coated with at least the first reagent portion chemically bonded to the surface of the substrate; d) Rinse the layer in the first reaction chamber with a first rinsing solution containing a first solvent to remove unreacted first reagent; e) The substrate from (d) is transferred via the conveying device to a second reaction chamber containing a second liquid solution, the second liquid solution containing at least a second reagent; f) Exposing the discrete substrate to the second liquid solution in the second reaction chamber via the conveying device, wherein the at least second reagent reacts with the at least first reagent chemically bonded to the surface of the discrete substrate to produce a monolayer of the artificial solid electrolyte interface coating on the surface of the discrete substrate, wherein the artificial solid electrolyte interface does not contribute to interparticle resistance, wherein the monolayer comprises a compound generated by the reaction of the at least second reagent with the first reagent; and g) Rinse the coating in the second reaction chamber with a second rinsing solution containing a second solvent to remove unreacted second reagent; The track conveying device mentioned above includes: a) A horizontal track located above the first and second reaction chambers and spanning the length of the first and second reaction chambers; and b) A vertical track attached to the horizontal track, the vertical track comprising an arm member driven by an arm motor configured to extend and retract in a substantially vertical direction and to be movable along the horizontal track in a substantially horizontal direction. The discrete substrate is connected to the vertical track, thereby allowing the discrete substrate to be conveyed to the first and second reaction chambers.

34. A battery pack, comprising: anode; cathode; A solid electrolyte or solid electrolyte-electrode composite matrix disposed between the anode and the cathode, wherein the solid electrolyte or the solid electrolyte-electrode composite matrix comprises an artificial solid electrolyte interface (SEI) layer produced by the method according to any one of claims 1-33; and A housing containing the anode, the cathode, the electrolyte, and a polymer separator, wherein the housing provides electrical contact with the anode and the cathode.

35. The battery pack of claim 34, further comprising a separator located between the anode and the cathode.

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