Electrochemical method for manufacturing a multilayer assembly that is adhesive and structurally stable

Abstract

An electrochemical method of making an adherent and structurally stable multilayer assembly, comprising: forming a metal intermediate layer on a base layer, electrochemically passivating some or all of the metal intermediate layer, thereby forming a binding layer comprising a binary oxide, and electrochemically growing a top oxide layer on the binding layer. The adherent and structurally stable multilayer assembly comprises: a binding layer on a base layer, the binding layer comprising a binary oxide; and a top oxide layer on the binding layer, the top oxide layer comprising a ternary oxide. The binding layer can be formed by electrochemical passivation of a metal intermediate layer on the base layer.

Description

[0001] Related applications

[0002] This patent document claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 617,210, filed January 3, 2024, pursuant to 35 USC119(e), and that provisional patent application is incorporated herein by reference in its entirety.

[0003] Federally funded research or development

[0004] This invention was made with government support under grant number 1449548 from the U.S. National Science Foundation. The government holds certain rights to this invention. Technical Field

[0005] This disclosure generally relates to methods for improving adhesion in multilayer components, and more specifically to electrochemical methods for preparing peel-resistant oxide films for battery electrodes and other applications. Background Technology

[0006] Lithium transition metal oxides (such as LiCoO2 (LCO)) are widely used as cathode materials in rechargeable lithium-ion batteries, which power electronic devices, electric vehicles, drones, power tools, medical devices, and other electronic components. Directly electrodeposited ceramic oxide (e.g., LCO) film cathodes for alkaline-ion batteries achieve higher gravimetric and volumetric energy density electrodes due to the absence of binders and additives. Cathode materials can be integrated with current collectors (such as battery-grade aluminum foil). Sufficient adhesion between the cathode material and the current collector is crucial for ensuring the mechanical integrity of the cathode during further processing and for successful operation in lithium-ion batteries. Unfortunately, electrodes can suffer from mechanical failure (debonding) at the metal-metal oxide interface, leading to severe peeling, loss of electron-ion pathways, and rapid degradation of electrochemical performance. Mechanical failure is a major obstacle to the application of electrodes in commercial lithium-ion or sodium-ion batteries. Currently, there is no universal strategy to improve the adhesion quality and peeling lifetime of electrochemically grown oxide films integrated with current collectors. Attached Figure Description

[0007] Figure 1A This is a schematic cross-sectional view of an exemplary adhesive and structurally stable multilayer component, wherein a bonding layer is formed on the metal intermediate layer due to passivation of only the surface region of the intermediate layer.

[0008] Figure 1B This is a schematic cross-sectional view of an exemplary adhesive and structurally stable multilayer component, wherein an adhesive layer is formed on a base layer or substrate due to the complete (through-thickness) passivation of the intermediate layer.

[0009] Figure 2This is a schematic cross-sectional view of an exemplary adhesive and structurally stable multilayer component, wherein the base layer includes a non-planar (curved) surface.

[0010] Figure 3 This is a schematic cross-sectional view of an exemplary adhesive and structurally stable multilayer component, wherein the base layer includes wires.

[0011] Figure 4A and Figure 4B This is a cross-sectional schematic diagram showing the mechanical integrity of the multilayer assembly and the adhesion between the layers, which can be independent of the extensional relationships (or absence) between the layers. Figure 4A This illustrates the strong crystal orientation (epitaxy) relationship between the metal interlayer and the substrate layer, and Figure 4B This shows that there is no crystal orientation (epitaxy) relationship between the metal intermediate layer and the base layer.

[0012] Figure 5A and Figure 5B This is a cross-sectional schematic diagram showing the mechanical integrity of the multilayer assembly and the adhesion between the layers, which can be independent of the texture of the top oxide outer layer.

[0013] Figure 6A Cyclic voltammetry curves of molten salt solutions (including LiOH-KOH-Co(OH)2) obtained at 275℃±5℃ with scan rates of 1 mV / s, 2 mV / s, 10 mV / s and 100 mV / s are shown, along with related scanning electron microscope (SEM) images from the multilayer assembly.

[0014] Figure 6B Cyclic voltammetry curves of molten salt solutions (including LiOH-KOH-Co(OH)2) obtained at scan rates of 1 mV / s, 2 mV / s, 10 mV / s and 100 mV / s at 300℃±5℃ are shown, along with related SEM images from multilayer modules.

[0015] Figure 6C Cyclic voltammetry curves of molten salt solutions (including LiOH-KOH-Co(OH)2) obtained at scan rates of 1 mV / s, 2 mV / s, 10 mV / s and 100 mV / s at 360 °C ± 5 °C are shown, along with related SEM images from the multilayer assembly.

[0016] Figures 7A-7F The current curves obtained from chronoamperometry experiments at various voltages (0.3 V, 0.4 V, 0.5 V, 0.6 V, 0.7 V, 0.8 V) for two different molten salt solution temperatures (300 °C and 360 °C) are shown; the curves are marked to indicate whether the passivation of the metal intermediate layer occurs alone or together with the growth of the top oxide layer.

[0017] Figure 8 SEM images and associated energy-dispersive X-ray spectroscopy (EDS) elemental maps of an adhesive multilayer assembly consisting of an aluminum substrate (50 μm), a nickel intermediate layer (2 μm), and an LCO top oxide layer (1000 μm) are shown.

[0018] Figure 9 SEM images and associated EDS elemental plots of an adhesive multilayer assembly consisting of a stainless steel substrate (27 μm), a nickel intermediate layer (2 μm), and an LCO top oxide layer (60 μm) are shown.

[0019] Figure 10 SEM images and associated EDS elemental maps of an adhesive multilayer assembly consisting of a carbon fiber woven paper substrate (5-10 μm), a nickel intermediate layer (1 μm), and an LCO top oxide layer (2 μm) are shown.

[0020] Figure 11 SEM images and associated EDS elemental maps of an adhesive multilayer assembly consisting of a titanium substrate (27 μm), a nickel intermediate layer (2–10 μm), and an LCO top oxide layer (60 μm) are shown.

[0021] Figure 12 SEM images of an adhesive multilayer assembly consisting of a stainless steel substrate (27 μm), a nickel intermediate layer (2–10 μm), and an LMO top oxide layer (60 μm) are shown.

[0022] Figure 13 SEM images of an adhesive multilayer assembly consisting of an aluminum substrate (27 μm), a nickel intermediate layer (2–10 μm), and an LMO top oxide layer (20 μm) are shown.

[0023] Figure 14 A schematic cross-sectional view, SEM image, and EDS elemental diagram of an adhesive multilayer assembly are shown. The assembly consists of a stainless steel substrate with a wire form factor (1 mm in diameter), a nickel intermediate layer (2 μm), and an LCO top oxide layer (500 μm).

[0024] Figure 15A This is a schematic diagram of an exemplary multilayer component evaluated under pure tension, and Figure 15B The relevant adhesion failure strength results are shown.

[0025] Figure 16A This is a schematic diagram of an exemplary multilayer component evaluated under pure shear, and Figure 16B The relevant adhesion failure strength results are shown. Detailed Implementation

[0026] This disclosure describes an electrochemical solution-based method for fabricating adhesive and structurally stable multilayer components. This method can be used to form multilayer components in which the adhesion of a metal oxide (“top oxide layer”) to a metal substrate plays a crucial role in controlling the functional properties of the component. Potential applications include: oxide films bonded to metal substrates for electrochemical energy storage (e.g., electrodes in Li-ion and Na-ion batteries), thermal barrier coatings, corrosion-resistant coatings, and / or oxide-based gas sensors integrated with metal substrates, where the quality of interfacial adhesion can alter or influence ion-electron transfer, heat transfer, accelerated localized chemical dissolution, and long-term structural stability at and across metal-metal oxide interfaces. The electrochemical method and the resulting adhesion quality have been demonstrated to be independent of the chemical composition, type, thickness, dimension, epitaxial relationship, and shape factor of the substrate and top oxide layer.

[0027] First, an electrochemical method for fabricating adhesive multilayer components is described in general terms, and then in more detail below. This method involves forming a metal interlayer on a substrate or base layer, electrochemically passivating some or all of the metal interlayer to form a bonding layer comprising a binary oxide, and then electrochemically growing a top oxide layer on the bonding layer. The bonding layer ensures strong adhesion of the top oxide layer and the structural integrity of the multilayer component. In some instances, only the surface portion of the metal interlayer undergoes electrochemical passivation, and the bonding layer is formed directly on the metal interlayer, such as... Figure 1A A cross-sectional schematic diagram is shown. In other examples, the entire metal interlayer undergoes electrochemical passivation, and the bonding layer is formed directly on the substrate or base layer, such as... Figure 1B A cross-sectional schematic diagram is shown. Advantageously, process conditions are controlled during electrochemical passivation to form a bonding layer without creating pinholes or physical gaps. Therefore, the bonding layer provides complete surface coverage of the metal interlayer and / or substrate, thereby promoting or ensuring strong interfacial adhesion across multilayer components. Experiments have shown that the interfacial adhesion strength of the multilayer components described in this disclosure can be at least 100 times that of conventional slurry-cast electrodes. The inventors have discovered that strong adhesion may require complete formation of the bonding layer and full surface coverage of the bonding layer prior to the growth of the top oxide layer, as described below.

[0028] The metal interlayer may comprise a metal capable of undergoing passivation to form an adhesive binary oxide to create a bonding layer. Suitable metals capable of forming thermally stable binary oxides include metals from Groups 3-12, Group 13 (Al, Ga, In, Tl, Nih); Group 14 (Si, Ge, Sn, Pb, Fl); Group 15 (As, Sb, Bi, Mc); and / or Group 16 (Se, Te, Po, Lv). Specific examples may include nickel, aluminum, cobalt, manganese, iron, and / or other late transition metals. The metal interlayer may be formed on a substrate by electroless deposition, electrochemical deposition, chemical vapor deposition, and / or physical vapor deposition (e.g., electron beam evaporation or sputtering). The metal interlayer may have a thickness ranging from 5 nm to 100 μm, or in some instances, from 5 nm to 5 μm. The bonding layer formed after passivation of the metal interlayer typically has a thickness ranging from 5 nm to 10 μm, or from 5 nm to 1 μm. The bonding layer may comprise a binary oxide selected from aluminum oxide, nickel oxide, cobalt oxide, manganese oxide, and iron oxide. Alternatively or concurrently, the binary oxide may be a transition metal oxide and / or may be formed from Group 13-16 metals (Al, Ga, In, Tl, Nh, Si, Ge, Sn, Pb, Fl, As, Sb, Bi, Mc, Se, Te, Po, and / or Lv). Advantageously, the binary oxide of the bonding layer has thermal stability of 1000°C or higher, where the term "thermal stability" refers to resistance to degradation or melting.

[0029] The substrate or base layer may contain metals and / or conductive materials, such as metals, alloys, conductive polymers, and / or conductive composites. For battery electrode applications, the substrate may serve as a current collector.

[0030] The top oxide formed on top of the bonding layer may comprise a ternary oxide. For battery electrode applications, the ternary oxide may comprise cathode materials, such as alkali metal (Li, Na, K) / alkaline earth metal (Ca, Mg) intercalated late transition group / group 13 / lower group 14-15 (Sn, Sb, Pb, Bi) oxides, individually, as a phase mixture, or as doped versions thereof. For example, the ternary oxide may comprise lithium or sodium combined with transition metals such as manganese or cobalt. Examples include lithium cobalt oxide, lithium manganese oxide, sodium cobalt oxide, and sodium manganese oxide. More specifically, the ternary metal oxide may comprise LiCoO2, NaCoO2, LiMnO2 or LiMn2O4, LiNi x Mn y Co z O2 and / or NaNi x Mn y Co zO2, where (x+y+z=1) and 0≤x,y,z≤1. For applications other than energy storage (such as thermal barrier coatings), other ternary oxides (such as yttrium-stabilized zirconium oxide (YSZ)) may be suitable. Typically, the top oxide layer has a thickness ranging from 5 nm to 2000 μm, or from 5 μm to 1000 μm.

[0031] In a specific example of an adhesive multilayer assembly, the top oxide layer may comprise a ternary metal oxide suitable for use as a cathode material in a lithium-ion or sodium-ion battery, such as LiCoO2, NaCoO2, LiMnO2, and / or LiMn2O4, the bonding layer may comprise nickel oxide, the metal intermediate layer may comprise nickel, and the substrate may comprise aluminum, stainless steel, titanium, and / or carbon.

[0032] In another specific example, the top oxide layer may comprise zirconium oxide (ZrO2) stabilized by yttrium oxide (Y2O3) (i.e., yttrium-stabilized zirconium oxide (YSZ)), the bonding layer may comprise Al2O3, the metal intermediate layer may comprise an MCrAlY alloy, where M is Ni and / or Co, and the substrate may comprise a turbine blade alloy, such as a nickel-based superalloy.

[0033] To perform some or all of the electrochemical passivation of the metal interlayer, the working electrode and the counter electrode can be immersed in an immersion containing oxygen-containing (O) groups. 2- ), hydroxyl (OH) - ) and / or peroxygen (O2) 2- In a non-aqueous bath for free radicals, the working electrode is understood to include a base layer (substrate) and a metal interlayer. The counter electrode may contain a conductive metal, such as nickel or cobalt, or other transition metals. Preferably, the counter electrode is electrochemically stable in the non-aqueous bath. In some instances, the counter electrode may be in the form of a foil, sheet, or foam. The non-aqueous bath can be described as a molten salt solution including an oxygen source. The molten salt solution may include a mixture of salts, as discussed below. For battery electrode applications, the molten salt solution may also include a Li, Na, K, Cs, Rb, Ca, or Mg source, and optionally include a transition metal source. In some instances, the molten salt solution may include one or more transition metal sources other than an oxygen source.

[0034] A voltage higher than the oxidation potential of the metal interlayer can be applied to the working electrode to achieve passivation. This voltage can also be lower than the deposition potential of the transition metal component (e.g., cobalt) of the top oxide layer to avoid simultaneous growth of the ternary oxide during passivation. The transition metal component can be a multivalent transition metal component for higher valence transitions (e.g., +2 to +3, +2 to +4). In one example, the voltage is in the range of about 0.35 V to about 0.45 V (relative to a Co reference electrode) to form a binary oxide. The applied voltage can be a constant voltage, and therefore the applied voltage can be described as a potentiostatic hold. In other examples, the applied voltage may include a constant current, a kinetic current, and / or a potentiostatic step. During the applied voltage, a non-water bath can be maintained at a controlled temperature as discussed below to ensure electrochemical passivation of the metal interlayer occurs before the growth of the top oxide. Typically, the voltage application lasts for a period of 2–5 minutes to passivate the metal interlayer and form a bonding layer containing the binary oxide.

[0035] Oxygen groups (O) in non-water bath or molten salt solutions 2- ), hydroxyl (OH) - ) and / or peroxygen (O2) 2- Free radicals can be generated by hydroxide ions (OH-). - ), halides (MX) n X = F, Cl, Br or I), nitrate (NO3) - ), nitrite (NO2) - ), sulfate (SO4 2- ), sulfite (SO3) 2- ), phosphate (PO4) 3- ), phosphate (HPO4) 2-The molten salt solution may be generated in situ by the electrochemical decomposition of acetate, carbonate, silicate, or aluminate / salts, or other suitable anions capable of generating oxygen / hydroxyl / peroxy radicals. The molten salt solution may include, for example, LiOH, KOH, KNO2, KNO3, NaOH, Na2O, NaNO3, NaNO2, Na2SO4, CsOH, Ba(OH)2, K2CO3, K2SO4, LiNO2, LiNO3, Li2CO3, LiCl, Li2O2, Li2SO4, and / or Li2CO3. In some instances, the molten salt solution may comprise a salt mixture containing LiOH-KOH, LiOH-NaOH, LiOH-NaOH-KOH-CsOH, NaOH-KOH, NaOH-CsOH, LiOH-Ba(OH)2, NaOH-KOH, Li2CO3-K2CO3, LiNO3-LiCl, or LiOH-Li2CO3. Alternatively, the salt mixture may contain Li2O-LiOH-KOH, Na2O-NaOH-NaOH, Li2O2-LiOH-KOH, Li2SO4-Na2SO4-K2SO4, LiNO3-NaNO3-KNO3, or LiNO2-NaNO2-KNO2.

[0036] Typically, the salt mixture comprises two or more hydroxides, such as lithium hydroxide and potassium hydroxide. The mass ratio of lithium hydroxide to potassium hydroxide can range from about 0.5:8.5 to about 1.5:7.5, for example, about 1:8 (or 1.875:15). For the use of the same non-water bath to form both the bonding layer and the top oxide layer, the salt mixture may also include a transition metal source, such as cobalt hydroxide. In such instances, the mass ratio can be 1.875:15:1 (LiOH:KOH:Co(OH)2), or more generally, the LiOH:KOH mass ratio can be from 1:2.67 to 1:16, and the KOH:Co(OH)2 mass ratio can be up to 10:1. It is advantageous to utilize eutectic mixtures of salts because the temperature required to melt the salt is lower at the eutectic composition, and thus the energy requirements of the process can be reduced. During electrochemical passivation / growth, the salt mixture is heated at a melting temperature equal to or higher than that of the mixture. In some instances, the temperature can range from 100°C to 800°C, but this temperature can be more tightly controlled (e.g., 350–800°C, or 350–365°C) to ensure that the electrochemical growth of the binary oxide (binding layer) is completed before the growth of the ternary (top) oxide. Cyclic voltammetry experiments described below demonstrate that electrochemical passivation of the metal interlayer at temperatures greater than 300°C (e.g., at least 330°C, or at least 350°C) and at suitable voltages results in complete (e.g., pinhole-free) surface coverage of the binary oxide on the metal interlayer / substrate without premature growth of the top oxide. In some instances, such as when using chloride salts, oxygenation of the non-water bath can be achieved by locally controlled release or injection of O2 gas (pure or as a mixture with inert gases Ar, N2) near the working electrode.

[0037] Electrochemical passivation of the metal interlayer to form a bonding layer and electrochemical growth of the top oxide layer can be performed sequentially in the same non-aqueous bath or in different non-aqueous baths. If the electrochemical growth of the top oxide layer is performed in the same non-aqueous bath as passivation, the voltage can be adjusted (e.g., increased) after passivation to achieve electrochemical growth of the ternary oxide on the bonding layer. For example, using the same molten salt solution used to form the bonding layer, the LCO top oxide layer can be initiated at a voltage equal to or higher than 0.46 V (relative to a cobalt reference electrode). For example, the voltage used to grow the top oxide layer can be in the range of 0.46 V to 1.2 V (relative to a cobalt reference electrode). Alternatively, a non-aqueous bath with a different chemical composition (e.g., further including a transition metal source) than the bath used to form the bonding layer can be used to grow the top oxide layer. In either case, the electrochemical conditions known in the art for preparing the top oxide layer can be used for electrodeposition. The method may also include an annealing step after the electrochemical formation of the top oxide layer to crystallize the ternary oxide. In some instances, annealing is performed at an annealing temperature in the range of about 600 °C to about 800 °C. At these temperatures, the adhesion strength does not change during annealing.

[0038] This method may involve electrochemical passivation and / or growth on planar or curved surfaces, such as Figure 2 A schematic cross-sectional view is shown. In some instances, the substrate or base layer may have a wire-like shape factor, on which a metallic intermediate layer (e.g., Ni) may be conformally grown and then passivated to form a bonding layer (e.g., NiO), followed by the electrochemical growth of a top oxide layer (e.g., LCO), as shown. Figure 3 A cross-sectional schematic diagram is shown. Alternatively, the substrate or base layer may have a foil shape factor, on which a metal interlayer, bonding layer, and top oxide layer are formed. Generally, the substrate or base layer may have any desired shape factor (morphology) and / or size. Experiments have shown that the radii of curvature of the individual layers (base layer, metal bonding layer, top oxide layer) do not affect the interfacial adhesion provided by the bonding layer and / or the structural integrity of the multilayer assembly.

[0039] In practice, the interfacial adhesion and structural integrity of the multilayer assembly provided by the bonding layer can be independent of the chemical composition and physical properties of the multilayer assembly. For example, interfacial adhesion and structural integrity can be independent of the materials selected for the substrate, metal interlayer, and top oxide layer. Interfacial adhesion and structural integrity can also, or alternatively, be independent of the thickness and / or roughness of the individual layers (substrate, metal interlayer, and top oxide layer) of the multilayer assembly. Interfacial adhesion and structural integrity can also, or alternatively, be independent of the epitaxial relationship (or its absence) between the substrate and the metal interlayer and / or between the metal interlayer and the top oxide layer; see, for example, [link to relevant documentation]. Figure 4AA cross-sectional schematic diagram (in which there is a strong orientation relationship between the metal interlayer and the substrate or base material) and Figure 4B A cross-sectional schematic diagram (where there is no orientation relationship between the metal interlayer and the substrate or base material). For example... Figure 5A and Figure 5B As shown, the interfacial adhesion provided by the bonding layer or the structural integrity of the multilayer assembly can be unaffected by the different textures of the top oxide layer.

[0040] Cyclic voltammetry and chronoamperometry experiments were conducted to investigate the effects of temperature and voltage on the formation of the adhesive bonding layer.

[0041] Figures 6A-6C The corresponding scanning electron microscope (SEM) images (500x magnification) and cyclic voltammetry curves of the electrodeposited samples after cyclic voltammetry experiments are shown, where “AG” indicates adhesive growth and “NAG” indicates non-adhesive growth. The cyclic voltammetry curves were obtained by scanning a typical molten salt plating solution (in this example, the salt mixture contains LiOH-KOH-Co(OH)2) at scan rates of 1 mV / s (black), 2 mV / s (red), 10 mV / s (green), and 100 mV / s (purple) at 275 °C. Figure 6A ), 300℃ Figure 6B ) and 360℃ Figure 6C The electrode configuration was obtained at ±5°C using a three-electrode setup (in this example, a Ni working electrode (comprising nickel on stainless steel (or Al, Ti, or C foam), a Ni counter electrode, and a cobalt reference electrode).

[0042] At 275℃ Figure 6A At a scan rate of only 1 mV / s (slow), adhesive growth of the binding layer was achieved, and at 300°C ( Figure 6B At 360°C, only scan rates of 1 mV / s and 2 mV / s resulted in adhesive growth. In contrast, at 360°C... Figure 6C Electrochemical passivation at the specified temperature resulted in adhesive growth at all scan rates (1 mV / s, 2 mV / s, 10 mV / s, and even 100 mV / s). Adhesive growth can be identified in cyclic voltammetry curves if the peak corresponding to a given scan rate is distinct rather than diffuse.

[0043] The key conclusion drawn from the experimental results is that at elevated temperatures (e.g., 360 °C), the nucleation and growth of the electrodeposited material are significantly enhanced, almost entirely thermodynamically controlled. In fact, this leads to extremely adhesive electrodeposition at both slow (1 mV / s) and very fast (100 mV / s) growth rates.

[0044] Chronoamperometry (current curves observed under continuous voltage) experiments were conducted at two bath temperatures (300℃ and 360℃) and different applied voltages (0.3 V, 0.4 V, 0.5 V, 0.6 V, 0.7 V, and 0.8 V (relative to a cobalt reference electrode (wire)) with a bath composition of LiOH, KOH, and Co(OH)₂ in a mass ratio of 1.875:15:1. The obtained current curves are shown below. Figures 7A to 7F In the figure, the legend for a single experiment is written as [Applied Voltage]_[Temperature (°C)]_[Mass of LiOH (g)], for example 0.3_300_37.5. SEM images of the top surface microstructure of the electrodeposited sample after the chronoamperometry experiment are provided below the corresponding current curve.

[0045] The key conclusions of the experimental results are: a constant potential of 0.4 V (relative to the Co wire) only leads to passivation (Ni to NiO oxidation). A constant potential above 0.4 V results in simultaneous passivation and electrocrystallization of LiCoO2, which in turn affects the growth quality, desired microstructure, and subsequent electrochemical performance of the electrodeposited material. A constant potential below 0.4 V results in incomplete surface passivation. Passivation at 0.4 V (relative to the Co reference electrode) at 360 °C results in complete surface passivation with the desired strength. Under the most preferred conditions, the voltage window is 0.4 V (+ / -0.05 V) for 2–4 minutes at a temperature of 360 °C or higher.

[0046] Example

[0047] Example 1. Adhesive LiCoO2 (top oxide layer) coating on planar aluminum (substrate layer)

[0048] A total of 400 g of KOH (reagent grade, ≥98%, anhydrous granules) was dried for 1 day in an Inconel crucible (250 mL capacity; Sigma) at 150 °C in a vacuum oven, and then heated to 360 °C on a hot plate in a glove box atmosphere filled with nitrogen or Ar (oxygen and water content <0.1 ppm) until the KOH solution was clear and dry. 25–125 g of LiOH (reagent grade, ≥98%, anhydrous granules) was added to the crucible, and the near-eutectic mixture was equilibrated at 360 °C. 7.5–30 g of cobalt hydroxide was slowly added to the melt while stirring with a spatula. After the cobalt hydroxide was completely dissolved, the solution was allowed to equilibrate for 8 hours.

[0049] Nickel (intermediate layer) coated aluminum foil (substrate / base layer) is used as the starting component for electrodeposition. Nickel is grown on the aluminum foil by electrodeposition / electrochemical deposition / chemical vapor deposition / sputtering or a continuous combination of one or more of the above.

[0050] In the first step, nickel-coated aluminum is immersed in a bath at a temperature of 360°C (at least 350°C but not exceeding 365°C), the bath being composed of LiOH, KOH and Co(OH)2 in a mass ratio of 1.875:15:1.

[0051] Formation of the bonding layer: In the next step, a chronoamperometry experiment (observing the current curve under continuous voltage) was conducted at a bath temperature of 360°C (the bath composition being LiOH, KOH, and Co(OH)₂ in a mass ratio of 1.875:15:1) with an applied voltage of 0.4 V (relative to the Co wire). Due to NiO as the intermediate phase... x The formation of the bonding layer, achieved by maintaining a constant potential at 360°C for 2-3 minutes, results in strong adhesion at the Ni-LCO (intermediate layer-top oxide layer) interface. It should be noted that this disclosure addresses NiO... x The reference may refer to stoichiometric nickel oxide (e.g., NiO) or non-stoichiometric nickel oxide, where x may, for example, be slightly higher or lower than 1. This treatment step is independent of the electrodeposition bath composition (LiOH-KOH-Co(OH)2). Following this treatment step, the assembly (substrate-intermediate-electrochemically formed bonding layer) is immersed in the desired electroplating solution for the final growth of LiCoO2.

[0052] Non-water bath composition: The stable bonding layer is formed by passivated NiO that completely covers the Ni surface without pinholes or physical gaps. x This is caused by the formation of layers. The non-water bath composition includes oxygen-based components (O) as part of a single component / eutectic solution / non-eutectic solution. 2- ) / hydroxyl (OH) - ) / peroxygen (O2) 2- Solvent. Oxygen / hydroxyl / peroxy radicals can pass through nitrate NO3. - nitrite NO2 - , sulfate (SO4 2- ), phosphate (PO4) 3- ), phosphate (HPO4) 2- It can be generated in situ by the electrochemical decomposition of any similar anions that generate oxygen / hydroxyl / peroxy radicals. The non-aqueous solvent can be oxygenated by the localized, controlled release of O2 gas (pure or as a mixture with inert gases Ar and N2) near the working electrode.

[0053] Single-tank and multi-tank synthesis: The final electrochemical growth of LiCoO2 can be carried out in the same / different plating solutions (one tank / multiple tanks) at any desired temperature by any or a combination of constant potential, potentiodynamic, constant current, kinetic current, and scan rate. Adhesion of the multilayer assembly is established during the formation of the bonding layer.

[0054] The final multilayer assembly following electrodeposition of the top layer of LCO is shown. Figure 8 The thickness of each layer is as follows: base layer: aluminum (50 μm), metal intermediate / bonding layer: nickel / NiO. x : 2 μm, top oxide layer: LCO: approximately 1000 μm. Scanning electron micrographs and superimposed EDS elemental maps elucidate the distinct multilayer structure, mechanical stability and continuity at the interfaces, and elemental distribution (Al from the substrate, Ni from the metal interlayer / bonding layer, and Co and O from LiCoO2).

[0055] Typical thicknesses of the top oxide layer: from a few nm to 2000 μm (e.g., 5 μm to 1000 μm). Examples include: LiCoO2 (2 μm, 60 μm, 500 μm, 1000 μm), LiMn2O4 (20 μm) and LiMnO2 (60 μm).

[0056] Typical substrate thickness: from a few nm to 2000 μm (e.g., 5 μm to 1000 μm). Examples: stainless steel (27 μm flat foil, 1000 μm diameter), Al (20 μm, 50 μm), C (10 μm), Ti (27 μm).

[0057] Nickel interlayer / NiO x Typical thickness of the bonding layer: a few nm to 100 μm (e.g., a few nm to 5 micrometers). Examples: nickel / nickel oxide (2 μm), manganese / manganese oxide (2 μm).

[0058] Typical thickness of the bonding layer formed by controlled electrochemical deposition: a few nm to 10 micrometers.

[0059] Example 2. Adhesive LiCoO2 (top oxide layer) coating on planar stainless steel (substrate layer)

[0060] The electrochemical process for forming the bonding layer is the same as in Example 1, but a stainless steel substrate is used.

[0061] Nickel is grown on stainless steel (SS) foil by electroless deposition / electrochemical deposition / chemical vapor deposition / sputtering or a combination of one or more of the above.

[0062] The final multilayer assembly following electrodeposition of the top layer of LCO is shown. Figure 9 The thickness of each layer is as follows: base layer: SS (27 μm), metal interlayer / bonding layer: nickel / NiO. x: 2 μm, top oxide layer: LCO: approximately 60 μm. Scanning electron micrographs and superimposed EDS elemental maps elucidate the distinct multilayer structure, mechanical stability and continuity at the interfaces, and elemental distribution (SS from the base layer, Ni from the intermediate / binding layer, and Co and O from LiCoO2).

[0063] Example 3. Adhesive LiCoO2 (top oxide layer) coating on porous carbon paper (substrate layer)

[0064] The electrochemical process for forming the bonding layer is the same as in Example 1, but the substrate used includes 3D carbon paper / conductive carbon particles / carbon nanotubes / carbon fibers / fullerenes / graphene / graphite / pyrolytic carbon and / or glassy carbon.

[0065] Nickel is grown on 3D carbon paper substrates by electroless deposition / electrochemical deposition / chemical vapor deposition / sputtering or a combination of one or more of the above.

[0066] The final multilayer assembly following the electrodeposition of the LCO top layer is shown. Figure 10 The thickness of each layer is as follows: base layer: carbon (5-10 μm), metal intermediate / bonding layer: nickel / NiO. x : 1 μm, top oxide layer: LCO: approximately 2 μm. Scanning electron micrographs and superimposed EDS elemental maps elucidate the distinct multilayer structure, mechanical stability and continuity at the interfaces, and elemental distribution (C from the base layer, Ni from the intermediate / binding layer, and Co and O from LiCoO2).

[0067] Example 4. Adhesive LiCoO2 (top oxide layer) coating on titanium (substrate layer)

[0068] The electrochemical process for forming the bonding layer is the same as in Example 1, but a titanium substrate is used. The LCO electroplating process for the top layer is the same.

[0069] Nickel is grown on Ti foil substrates by electroless deposition / electrochemical deposition / chemical vapor deposition / sputtering or a combination of one or more of the above.

[0070] The final multilayer assembly following the electrodeposition of the LCO top layer is shown. Figure 11 The thickness of each layer is as follows: base layer: titanium (27 μm), metal intermediate / bonding layer: nickel / NiO. x : 2-10 μm, top oxide layer: LCO: approximately 60 μm. Scanning electron micrographs and superimposed EDS elemental maps elucidate the distinct multilayer structure, mechanical stability and continuity at the interfaces, and elemental distribution (titanium from the substrate, Ni from the intermediate / bonding layer, and Co and O from LiCoO2).

[0071] Example 5. Adhesive LiMnO2 (top oxide layer) coating on stainless steel (substrate layer)

[0072] A total of 400 g of KOH (reagent grade, ≥98%, anhydrous granules) was dried for 1 day in an Inconel crucible (250 mL capacity; Sigma) at 150 °C in a vacuum oven, and then heated to 360 °C on a hot plate in a glove box atmosphere filled with nitrogen or Ar (oxygen and water content <0.1 ppm) until the KOH solution was clear and dry. 25–100 g of LiOH (reagent grade, ≥98%, anhydrous granules) was added to the crucible, and the near-eutectic mixture was equilibrated at 360 °C. 10–50 g of manganese chloride was slowly added to the melt while stirring with a spatula. After the manganese chloride was completely dissolved and complexed, the solution was equilibrated for 8 hours.

[0073] Nickel (metallic interlayer) coated stainless steel foil (substrate / base layer) is used as the starting component for electrodeposition. Nickel is grown on the stainless steel foil by electrodeposition / electrochemical deposition / chemical vapor deposition / sputtering or a continuous combination of one or more of the above.

[0074] In the first step, nickel-coated stainless steel is immersed in a bath at 360°C (at least 350°C but not exceeding 365°C), the bath being composed of LiOH, KOH and Mn(Cl)2 in a mass ratio of 1.875:15:1.

[0075] Formation of the bonding layer: In the next step, an adhesive bonding layer is grown at 0.4 V (relative to the Co filament) for 3-5 minutes. The specific type / composition of the bath used for the seed layer is not important for adhesion. Typically, the same bath composition as the top oxide layer deposition step is chosen. This is because NiO acts as an intermediate phase. x and MnO x The formation of the bonding layer involves maintaining a constant potential at 360°C for 2-3 minutes to induce strong adhesion at the Ni-LiMnO2 (intermediate layer-top oxide layer) interface. This treatment step is independent of the electrodeposition bath composition (LiOH-KOH-Mn(Cl)2). Following this treatment step, the assembly (substrate layer-intermediate layer-electrochemically formed bonding layer) is immersed in the desired electroplating solution for the final growth of LiMnO2.

[0076] Single-tank and multi-tank synthesis: The final electrochemical growth of LiMnO2 can be carried out in the same or different plating solutions (one tank or multiple tanks) at any desired temperature by any or a combination of constant potential, potentiodynamic, constant current, dynamic current, and scan rate. Adhesion of the multilayer assembly is established during the formation of the bonding layer.

[0077] The final multilayer assembly following the electrodeposition of the LiMnO2 top layer is shown. Figure 12In the SEM image, the thickness of each layer is as follows: substrate layer: SS (27 μm), intermediate / bonding layer: nickel / NiO. x : 2-10 μm, top oxide layer: LiMnO2: approximately 60 μm. Scanning electron micrographs and superimposed EDS elemental maps elucidate the distinct multilayer structure, mechanical stability and continuity at the interfaces, and elemental distribution (Fe from the base layer, Ni from the intermediate / binding layer, and Mn and O from LiMnO2).

[0078] Example 6. Adhesive LiMn2O4 (top oxide layer) coating on aluminum foil (substrate layer)

[0079] A total of 400 g of NaOH (reagent grade, ≥98%, anhydrous granules) was dried for 1 day in an Inconel crucible (250 mL capacity; Sigma) at 150 °C in a vacuum oven, and then heated to 360 °C on a hot plate in a glove box atmosphere filled with nitrogen or Ar (oxygen and water content <0.1 ppm) until the NaOH solution was clear and dry. 7.5–30 g of manganese chloride was slowly added to the melt while stirring with a spatula. After the MnCl2 / Mn3O4 was completely dissolved and complexed, the solution was allowed to equilibrate for 8 hours.

[0080] Nickel (intermediate layer) coated Al foil (substrate / base layer) is used as the starting component for electrodeposition. Nickel is grown on the Al foil by electrodeposition / electrochemical deposition / chemical vapor deposition / sputtering or a continuous combination of one or more of the above.

[0081] In the first step, nickel-coated stainless steel is immersed in a bath at 360°C (at least 350°C but not exceeding 365°C) composed of NaOH and Mn(Cl)₂. In the next step, an adhesive bonding layer is grown at 0.4 V (relative to the Co wire) for 3–5 minutes. The specific type / composition of the bath used for the seed layer is not critical for adhesion. Typically, the same bath composition as the top oxide layer deposition step is chosen.

[0082] Formation of the bonding layer: A chronoamperometry experiment (observing the current curve under continuous voltage) was conducted with an applied voltage of 0.4 V (relative to the Co wire), in which NiO, as an intermediate phase, was used. x The formation of the bonding layer involves maintaining a constant potential at 360°C for 2-3 minutes to induce strong adhesion at the Ni-NaMnO2 (intermediate layer-top oxide layer) interface. This treatment step is independent of the electrodeposition bath composition (NaOH-MnCl2). Following this treatment step, the assembly (substrate layer-intermediate layer-electrochemically formed bonding layer) is immersed in the desired electroplating solution for the final growth of NaMnO2.

[0083] Single-tank and multi-tank synthesis:The final electrochemical growth of NaMnO2 can be carried out in the same / different electroplating solutions (one tank / multiple tanks) at any desired temperature by any or a combination of constant potential, potentiodynamic, constant current, kinetic current, and scan rate. Adhesion of the multilayer assembly is established during the formation of the bonding layer.

[0084] The deposited NaMnO2 was immersed in a low-melting eutectic ion exchange medium (LiCl-LiNO3 1 / 5w / w) at 450°C for 2 hours, and then further annealed at 600°C for 6 hours to convert NaMnO2 into LiMn2O4.

[0085] The final multilayer assembly following electrodeposition of the LiMn2O4 top layer is shown. Figure 13 In the SEM image, the thicknesses of each layer are: base layer: aluminum (20 μm), intermediate / bonding layer: nickel / NiO. x : 2 μm, top oxide layer: LiMn2O4: approximately 20 μm. Scanning electron micrographs and superimposed EDS elemental maps elucidate the distinct multilayer structure, mechanical stability and continuity at the interfaces, and elemental distribution (Al from the base layer, Ni from the intermediate / binding layer, and Mn and O from LiMn2O4).

[0086] Example 7. Adhesive LiCoO2 (top oxide layer) coating on stainless steel wire (substrate layer)

[0087] A total of 400 g of KOH (reagent grade, ≥98%, anhydrous granules) was dried for 1 day in an Inconel crucible (250 mL capacity; Sigma) at 150 °C in a vacuum oven, and then heated to 360 °C on a hot plate in a glove box atmosphere filled with nitrogen or Ar (oxygen and water content <0.1 ppm) until the KOH solution was clear and dry. 25–100 g of LiOH (reagent grade, ≥98%, anhydrous granules) was added to the crucible, and the near-eutectic mixture was equilibrated at 360 °C. 7.5–30 g of cobalt hydroxide was slowly added to the melt while stirring with a spatula. After the cobalt hydroxide was completely dissolved and complexed, the solution was allowed to equilibrate for 8 hours.

[0088] Nickel (intermediate layer) coated stainless steel wire (substrate / base layer) is used as the starting component for electrodeposition. Nickel is grown on stainless steel foil by electrodeposition / electrochemical deposition / chemical vapor deposition / sputtering or a continuous combination of one or more of the above.

[0089] In the first step, nickel-coated stainless steel is immersed in a bath at 360°C (at least 350°C but not exceeding 365°C) with a composition of LiOH, KOH, and cobalt hydroxide in a mass ratio of 1.875:15:1. In the next step, an adhesive bonding layer is grown at 0.4 V (relative to the Co filament) for 3–5 minutes. The specific type / composition of the bath used for the seed layer is not critical for adhesion. Typically, the same bath composition as the top oxide layer deposition step is chosen.

[0090] Formation of the bonding layer: A chronoamperometry experiment (current curve observed under continuous voltage) was conducted at a bath temperature of 360℃ with an applied voltage of 0.4 V (relative to the Co wire). The bath composition consisted of LiOH, KOH, and Co(OH)₂ in a mass ratio of 1.875:15:1. NiO, as an intermediate phase... x The formation of the bonding layer involves maintaining a constant potential at 360°C for 2-3 minutes to induce strong adhesion at the Ni-LCO (intermediate layer-top oxide layer) interface. This treatment step is independent of the electrodeposition bath composition (LiOH-KOH-Co(OH)2). Following this treatment step, the assembly (substrate layer-intermediate layer-electrochemically formed bonding layer) is immersed in the desired electroplating solution for the final growth of LiCoO2.

[0091] Single-tank and multi-tank synthesis: The final electrochemical growth of LiCoO2 can be carried out in the same / different plating solutions (one tank / multiple tanks) at any desired temperature by any or a combination of constant potential, potentiodynamic, constant current, kinetic current, and scan rate. Adhesion of the multilayer assembly is established during the formation of the bonding layer.

[0092] The final multilayer assembly following electrodeposition of the LCO top layer is composed of... Figure 14 The schematic diagram, SEM image, and EDS are overlaid. The thickness of each layer is as follows: Base layer: Stainless steel: 1 mm diameter wire; Intermediate / bonding layer: Nickel / NiO x : 2 μm, top oxide layer: LCO: approximately 500 μm. Scanning electron micrographs and superimposed EDS elemental maps elucidate the distinct multilayer structure, mechanical stability and continuity at the interfaces, and elemental distribution (Fe from the base layer, Ni from the intermediate / binding layer, and Co and O from LiCoO2).

[0093] Example 8. Evaluation of adhesion failure strength in electrodeposited multilayer modules

[0094] The adhesion failure strength of electrodeposited multilayer assemblies comprising: (1) a 28 μm stainless steel (substrate), approximately 250 nm nickel / nickel oxide (intermediate / bonding layer), and 70 μm LiCoO2 (top oxide layer); (2) a 20 μm aluminum (substrate), approximately 250 nm nickel / nickel oxide (intermediate / bonding layer), and 40 μm LiCoO2 (top oxide layer); and (3) a 28 μm stainless steel (substrate), approximately 250 nm nickel / nickel oxide (intermediate / bonding layer), and 250 μm LiCoO2 (top oxide layer) were evaluated and compared with the adhesion failure strength of slurry-cast LCOs prepared using conventional manufacturing methods.

[0095] The lower limit of adhesion failure strength in multilayer components is assessed by pure tensile testing (direct tension test), such as... Figure 15A As shown. For multilayer components designed for use in lithium-ion and sodium-ion batteries, the lower tensile strength is at least about 10.4 MPa. Figure 15B For conventional slurry-cast materials used in commercial lithium-ion and sodium-ion battery cathodes and anodes, the adhesion strength is approximately 84.3 kPa. The adhesion strength of the multilayer components produced by this method is at least 100 times that of the interfacial adhesion strength of conventional slurry-cast electrodes.

[0096] The lower limit of adhesion failure strength in multilayer components is evaluated using pure shear (interfacial shear test), such as... Figure 16A As shown. For multilayer components designed for use in lithium-ion and sodium-ion batteries, the lower tensile strength is at least about 18.9 MPa. Figure 16B For conventional slurry casting materials used in the cathodes and anodes of commercial lithium-ion and sodium-ion batteries, the adhesion strength is approximately 3.27 MPa. 3 .

[0097] The topics described in this disclosure may include the following aspects:

[0098] The first aspect relates to an electrochemical method for manufacturing an adhesive and structurally stable multilayer component, the method comprising: forming a metal interlayer on a substrate layer; electrochemically passivating some or all of the metal interlayer to form a bonding layer comprising a binary oxide; and electrochemically growing a top oxide layer on the bonding layer.

[0099] The second aspect relates to the electrochemical method of the first aspect, wherein only the surface portion of the metal interlayer undergoes electrochemical passivation.

[0100] The third aspect relates to any of the aforementioned electrochemical methods, wherein the entire metal interlayer undergoes electrochemical passivation.

[0101] The fourth aspect relates to any of the aforementioned electrochemical methods, wherein the bonding layer is formed without pinholes or physical gaps, and / or wherein the bonding layer provides full surface coverage of the metal intermediate layer and / or the substrate layer.

[0102] The fifth aspect relates to any of the electrochemical methods described above, wherein the interfacial adhesion provided by the binding layer and the structural integrity of the multilayer assembly are independent of one or more chemical or physical properties of the multilayer assembly.

[0103] The sixth aspect relates to an electrochemical method of the foregoing aspects, wherein one or more of the chemical or physical properties are selected from: the material used for the substrate, the metal intermediate layer, and the top oxide layer; the thickness and / or roughness of the substrate, the metal intermediate layer, and / or the top oxide layer; the interfacial epitaxial relationship between the substrate and the metal intermediate layer and / or between the metal intermediate layer and the top oxide layer, or its absence; and the texture of the top oxide layer.

[0104] The seventh aspect relates to any of the electrochemical methods described in the foregoing aspects, wherein the binary oxide is selected from: aluminum oxide, nickel oxide, cobalt oxide, manganese oxide and iron oxide, and / or the binary oxide comprises transition metal oxides and / or includes group 13-16 metals (Al, Ga, In, Tl, Nh, Si, Ge, Sn, Pb, Fl, As, Sb, Bi, Mc, Se, Te, Po and / or Lv).

[0105] The eighth aspect relates to any of the electrochemical methods described above, wherein the binding layer has a thickness in the range of 5 nm to 10 μm or 5 nm to 1 μm.

[0106] The ninth aspect relates to any of the foregoing electrochemical methods, wherein the substrate layer comprises a metal and / or conductive material selected from the group consisting of metals, alloys, conductive polymers, and conductive composite materials.

[0107] The tenth aspect relates to any of the aforementioned electrochemical methods, wherein the top oxide layer comprises a ternary oxide.

[0108] The eleventh aspect relates to any of the aforementioned electrochemical methods, wherein the top oxide layer comprises alkali metal group (Li, Na, K) / alkaline earth metal group (Ca, Mg) intercalated post-transition group / group 13 / lower group 14-15 (Sn, Sb, Pb, Bi) oxides, individually, as a phase mixture, or as doped versions thereof.

[0109] The twelfth aspect relates to any of the foregoing electrochemical methods, wherein the top oxide layer comprises a ternary oxide selected from the group consisting of: LiCoO2, NaCoO2, LiMnO2, LiMn2O4, and LiNi. x Mn y Co z O2 and NaNi x Mn y Co z O2, where (x+y+z=1) and 0≤x,y,z≤1.

[0110] The thirteenth aspect relates to any of the electrochemical methods described above, wherein the top oxide layer has a thickness in the range of 5 nm to 2000 μm or 5 μm to 1000 μm.

[0111] The fourteenth aspect relates to any of the aforementioned electrochemical methods, wherein the metal interlayer comprises a metal capable of forming the binary oxide, and wherein the binary oxide has thermal stability of 1000°C or higher.

[0112] The fifteenth aspect relates to any of the aforementioned electrochemical methods, wherein forming the metal intermediate layer on the substrate includes electroless deposition, electrochemical deposition, chemical vapor deposition, and / or physical vapor deposition.

[0113] The sixteenth aspect relates to any of the aforementioned electrochemical methods, wherein the metal interlayer has a thickness in the range of 5 nm to 100 μm or 5 nm to 5 μm.

[0114] The seventeenth aspect relates to any of the foregoing electrochemical methods, wherein electrochemical passivation of some or all of the metal interlayer comprises: immersing the working electrode and the counter electrode in a non-aqueous bath, said non-aqueous bath containing oxygen (O) groups. 2- ), hydroxyl (OH) - ) and / or peroxygen (O2) 2- The working electrode contains a base layer having the metal interlayer thereon, the non-water bath is at a temperature of at least 330°C; and a voltage higher than the oxidation potential of the metal interlayer is applied to the working electrode.

[0115] The eighteenth aspect relates to the electrochemical method of the foregoing aspects, wherein the temperature is in the range of 350°C to 365°C.

[0116] The nineteenth aspect relates to any of the electrochemical methods described above, wherein applying the voltage includes maintaining a constant potential.

[0117] The twentieth aspect relates to any of the aforementioned electrochemical methods, wherein applying the voltage includes constant current, dynamic current and / or potentiodynamic steps.

[0118] The twenty-first aspect relates to any of the electrochemical methods described above, wherein the voltage is lower than the deposition potential of the transition metal component of the top oxide layer, the transition metal component being a multivalent transition metal component with a higher valence state transition (e.g., +2 to +3, +2 to +4).

[0119] The twenty-second aspect relates to any of the electrochemical methods described above, wherein the voltage relative to the Co reference electrode is in the range of about 0.35 V to about 0.45 V.

[0120] The twenty-third aspect relates to any of the electrochemical methods described above, wherein the non-aqueous bath comprises a molten salt solution comprising a source of Li, Na, K, Cs, Rb, Ca, or Mg and optionally a transition metal source.

[0121] The twenty-fourth aspect relates to any of the electrochemical methods described in the foregoing aspects, wherein the molten salt solution comprises one or more salts selected from the following: LiOH, KOH, KNO2, KNO3, NaOH, Na2O, NaNO3, NaNO2, Na2SO4, CsOH, Ba(OH)2, K2CO3, K2SO4, LiNO2, LiNO3, Li2CO3, LiCl, Li2O2, Li2SO4, and Li2CO3.

[0122] The twenty-fifth aspect relates to any of the electrochemical methods described above, wherein the molten salt solution comprises a mixture of salts selected from the following: LiOH-KOH, LiOH-NaOH, LiOH-NaOH-KOH-CsOH, NaOH-KOH, NaOH-CsOH, LiOH-Ba(OH)2, NaOH-KOH, Li2CO3-K2CO3, LiNO3-LiCl, and LiOH-Li2CO3.

[0123] The twenty-sixth aspect relates to any of the foregoing electrochemical methods, wherein the molten salt solution comprises a mixture of salts selected from the following: Li2O-LiOH-KOH, Na2O-NaOH-NaOH, Li2O2-LiOH-KOH, Li2SO4-Na2SO4-K2SO4, LiNO3-NaNO3-KNO3, and LiNO2-NaNO2-KNO2.

[0124] The twenty-seventh aspect relates to any of the electrochemical methods described in the foregoing aspects, wherein the oxygen (O) group 2- ), hydroxyl (OH) - ) and / or peroxygen (O2) 2- Free radicals pass through hydroxide ions (OH-) - ), halides (MX) n X = F, Cl, Br or I), nitrate (NO3)- ), nitrite (NO2) - ), sulfate (SO4 2- ), sulfite (SO3) 2- ), phosphate (PO4) 3- ), phosphate (HPO4) 2- It is generated in situ through the electrochemical decomposition of acetate, carbonate, silicate, aluminate or other anions.

[0125] The twenty-eighth aspect relates to any of the aforementioned electrochemical methods, and further includes oxygenating the non-water bath by controlled release or injection of a gas containing O2 near the working electrode.

[0126] The twenty-ninth aspect relates to any of the aforementioned electrochemical methods, and further includes an annealing treatment to crystallize the top oxide layer.

[0127] The thirtieth aspect relates to any of the electrochemical methods described above, wherein the top oxide layer comprises LiCoO2, NaCoO2, LiMnO2 and / or LiMn2O4; the bonding layer comprises nickel oxide; the metal intermediate layer comprises nickel; and the base layer comprises aluminum, stainless steel, titanium and / or carbon.

[0128] The thirty-second aspect relates to any of the electrochemical methods described above, wherein the top oxide layer comprises yttrium oxide (Y2O3) stabilized zirconium oxide (ZrO2); the bonding layer comprises Al2O3; the metal intermediate layer comprises an MCrAlY alloy, wherein M is Ni and / or Co; and the base layer comprises a turbine blade alloy.

[0129] The thirty-third aspect relates to any of the electrochemical methods described above, wherein the substrate layer comprises a plane.

[0130] The thirty-fourth aspect relates to any of the aforementioned electrochemical methods, wherein the substrate layer comprises a curved surface.

[0131] The thirty-fifth aspect relates to any of the aforementioned electrochemical methods, wherein the substrate layer has a wire shape factor.

[0132] The thirty-sixth aspect relates to an adhesive and structurally stable multilayer component comprising: a bonding layer on a substrate layer, the bonding layer comprising a binary oxide; and a top oxide layer on the bonding layer, the top oxide layer comprising a ternary oxide.

[0133] The thirty-seventh aspect relates to a multilayer component of the foregoing aspects, wherein the bonding layer is formed by electrochemical passivation of a metal interlayer on the substrate layer.

[0134] The thirty-eighth aspect relates to any of the aforementioned multilayer components, wherein the bonding layer is free of pinholes or physical gaps, and / or wherein the bonding layer provides full surface coverage of the metal intermediate layer and / or the base layer.

[0135] The thirty-ninth aspect relates to any of the multilayer components of the foregoing aspects, wherein the binary oxide is selected from: aluminum oxide, nickel oxide, cobalt oxide, manganese oxide and iron oxide, and / or wherein the binary oxide comprises transition metal oxides and / or comprises group 13-16 metals (Al, Ga, In, Tl, Nh, Si, Ge, Sn, Pb, Fl, As, Sb, Bi, Mc, Se, Te, Po and / or Lv).

[0136] The fortieth aspect relates to any of the aforementioned multilayer components, wherein the bonding layer has a thickness in the range of 5 nm to 10 μm or 5 nm to 1 μm.

[0137] The forty-first aspect relates to any of the foregoing aspects of a multilayer assembly, wherein the substrate layer comprises a metal and / or conductive material selected from the group consisting of metals, alloys, conductive polymers, and conductive composite materials.

[0138] The forty-second aspect relates to any of the aforementioned multilayer components, wherein the top oxide layer comprises a ternary oxide.

[0139] The forty-third aspect relates to any of the aforementioned multilayer components, wherein the top oxide layer comprises alkali metal group (Li, Na, K) / alkaline earth metal group (Ca, Mg) intercalated post-transition group / group 13 / lower group 14-15 (Sn, Sb, Pb, Bi) oxides, individually, as a phase mixture, or as doped versions thereof.

[0140] The forty-fourth aspect relates to any of the foregoing multilayer components, wherein the top oxide layer comprises a ternary oxide selected from the group consisting of: LiCoO2, NaCoO2, LiMnO2, LiMn2O4, and LiNi. x Mn y Co z O2 and NaNi x Mn y Co z O2, where (x+y+z=1) and 0≤x,y,z≤1.

[0141] The forty-fifth aspect relates to any of the aforementioned multilayer components, wherein the top oxide layer has a thickness in the range of 5 nm to 2000 μm or 5 μm to 1000 μm.

[0142] The forty-sixth aspect relates to any of the foregoing multilayer components, wherein the top oxide layer comprises LiCoO2, NaCoO2, LiMnO2 and / or LiMn2O4; the bonding layer comprises nickel oxide; and the base layer comprises aluminum, stainless steel, titanium and / or carbon.

[0143] The forty-seventh aspect relates to any of the aforementioned multilayer components, wherein the top oxide layer comprises yttrium oxide (Y2O3) stabilized zirconium oxide (ZrO2); the bonding layer comprises Al2O3; and the base layer comprises a turbine blade alloy.

[0144] The forty-eighth aspect relates to any of the aforementioned multilayer components, wherein the base layer comprises a plane.

[0145] The forty-ninth aspect relates to any of the aforementioned multilayer components, wherein the base layer comprises a curved surface.

[0146] The fiftieth aspect relates to any of the aforementioned multilayer components, wherein the base layer has a wire shape factor.

[0147] The fifty-first aspect relates to any of the aforementioned multilayer components, wherein the top oxide layer comprises a cathode material and the base layer comprises a current collector for a lithium-ion or sodium-ion battery.

[0148] The fifty-second aspect relates to any of the foregoing multilayer components, wherein the top oxide layer comprises a thermal barrier coating, an anti-corrosion coating and / or an oxide-based gas sensor, and wherein the base layer comprises a metal substrate.

[0149] Although the invention has been described in great detail with reference to certain embodiments, other embodiments are possible without departing from the invention. Therefore, the spirit and scope of the appended claims should not be limited to the description of the preferred embodiments contained herein. All embodiments falling within the meaning of the claims, whether literal or equivalent, are intended to be included therein.

[0150] Furthermore, the advantages described above are not necessarily the only advantages of the present invention, and it is not necessarily expected that every embodiment of the present invention will achieve all the advantages described.

Claims

1. An electrochemical method for manufacturing adhesive and structurally stable multilayer components, the method comprising: A metallic interlayer is formed on the substrate layer; Electrochemical passivation of some or all of the metal interlayer is performed to form a bonding layer containing binary oxides; and An oxide layer is electrochemically grown on the bonding layer.

2. The electrochemical method according to claim 1, wherein only the surface portion of the metal interlayer undergoes electrochemical passivation.

3. The electrochemical method according to claim 1, wherein the entire metal interlayer undergoes electrochemical passivation.

4. The electrochemical method according to claim 1, wherein the bonding layer is formed without pinholes or physical gaps, and / or The bonding layer provides full surface coverage of the metal intermediate layer and / or the base layer.

5. The electrochemical method of claim 1, wherein the interfacial adhesion provided by the bonding layer and the structural integrity of the multilayer assembly are independent of one or more chemical or physical properties of the multilayer assembly.

6. The electrochemical method according to claim 5, wherein the one or more chemical or physical properties are selected from: Materials used for the base layer, the metal intermediate layer, and the top oxide layer; The thickness and / or roughness of the base layer, the metal intermediate layer and / or the top oxide layer; The epitaxial relationship between the base layer and the metal intermediate layer and / or between the metal intermediate layer and the top oxide layer, or its absence; and The texture of the top oxide layer.

7. The electrochemical method according to claim 1, wherein the binary oxide is selected from: aluminum oxide, nickel oxide, cobalt oxide, manganese oxide, and iron oxide, and / or The binary oxide is a transition metal oxide and / or formed from group 13-16 metals (Al, Ga, In, Tl, Nh, Si, Ge, Sn, Pb, Fl, As, Sb, Bi, Mc, Se, Te, Po and / or Lv).

8. The electrochemical method according to claim 1, wherein the bonding layer has a thickness in the range of 5 nm to 10 μm or 5 nm to 1 μm.

9. The electrochemical method according to claim 1, wherein the substrate layer comprises a metal and / or conductive material selected from the group consisting of metals, alloys, conductive polymers, and conductive composite materials.

10. The electrochemical method of claim 1, wherein the top oxide layer comprises a ternary oxide.

11. The electrochemical method according to claim 1, wherein the top oxide layer comprises alkali metal group (Li, Na, K) / alkaline earth metal group (Ca, Mg) intercalated post-transition group / group 13 / lower group 14-15 (Sn, Sb, Pb, Bi) oxides, individually, as a phase mixture, or as doped versions thereof.

12. The electrochemical method according to claim 1, wherein the top oxide layer comprises a ternary oxide selected from the group consisting of: LiCoO2, NaCoO2, LiMnO2, LiMn2O4, and LiNi. x Mn y Co z O2 and NaNi x Mn y Co z O2, where (x+y+z=1) and 0≤x,y,z≤1.

13. The electrochemical method according to claim 1, wherein the top oxide layer has a thickness in the range of 5 nm to 2000 μm or 5 μm to 1000 μm.

14. The electrochemical method of claim 1, wherein the metal interlayer comprises a metal capable of forming the binary oxide, and The binary oxide described therein has thermal stability of 1000°C or higher.

15. The electrochemical method according to claim 1, wherein forming the metal intermediate layer on the substrate comprises electroless deposition, electrochemical deposition, chemical vapor deposition and / or physical vapor deposition.

16. The electrochemical method according to claim 1, wherein the metal interlayer has a thickness in the range of 5 nm to 100 μm or 5 nm to 5 μm.

17. The electrochemical method of claim 1, wherein electrochemical passivation of some or all of the metal interlayer comprises: The working electrode and the counter electrode are immersed in a non-aqueous bath containing oxygen (O) groups. 2- ), hydroxyl (OH) - ) and / or peroxygen (O2) 2- (Free radicals), the working electrode includes the base layer having the metal intermediate layer thereon, and the non-water bath is at a temperature of at least 330°C; and A voltage higher than the oxidation potential of the metal interlayer is applied to the working electrode.

18. The electrochemical method according to claim 17, wherein the temperature is in the range of 350°C to 365°C.

19. The electrochemical method of claim 17, wherein applying the voltage comprises maintaining a constant potential.

20. The electrochemical method of claim 17, wherein applying the voltage includes constant current, dynamic current and / or potentiodynamic steps.

21. The electrochemical method of claim 17, wherein the voltage is lower than the deposition potential of the transition metal component of the top oxide layer.

22. The electrochemical method of claim 17, wherein the voltage relative to the Co reference electrode is in the range of about 0.35 V to about 0.45 V.

23. The electrochemical method of claim 17, wherein the non-aqueous bath comprises a molten salt solution comprising a source of Li, Na, K, Cs, Rb, Ca, or Mg, and optionally a transition metal source.

24. The electrochemical method according to claim 23, wherein the molten salt solution comprises one or more salts selected from the following: LiOH, KOH, KNO2, KNO3, NaOH, Na2O, NaNO3, NaNO2, Na2SO4, CsOH, Ba(OH)2, K2CO3, K2SO4, LiNO2, LiNO3, Li2CO3, LiCl, Li2O2, Li2SO4, and Li2CO3.

25. The electrochemical method according to claim 23, wherein the molten salt solution comprises a mixture of salts selected from the following: LiOH-KOH, LiOH-NaOH, LiOH-NaOH-KOH-CsOH, NaOH-KOH, NaOH-CsOH, LiOH-Ba(OH)2, NaOH-KOH, Li2CO3-K2CO3, LiNO3-LiCl, and LiOH-Li2CO3.

26. The electrochemical method according to claim 23, wherein the molten salt solution comprises a mixture of salts selected from the following: Li2O-LiOH-KOH, Na2O-NaOH-NaOH, Li2O2-LiOH-KOH, Li2SO4-Na2SO4-K2SO4, LiNO3-NaNO3-KNO3, and LiNO2-NaNO2-KNO2.

27. The electrochemical method according to claim 17, wherein the oxygen group (O) 2- ), hydroxyl (OH) - ) and / or peroxygen (O2) 2- Free radicals pass through hydroxide ions (OH-) - ), halides (MX) n X = F, Cl, Br or I), nitrate (NO3) - ), nitrite (NO2) - ), sulfate (SO4 2- ), sulfite (SO3) 2- ), phosphate (PO4) 3- ), phosphate (HPO4) 2- It is generated in situ through the electrochemical decomposition of acetate, carbonate, silicate, aluminate or other anions.

28. The electrochemical method of claim 17 further comprises oxygenating the non-water bath by controlled release or injection of a gas containing O2 near the working electrode.

29. The electrochemical method of claim 1 further comprises an annealing treatment to crystallize the top oxide layer.

30. The electrochemical method according to claim 1, wherein the top oxide layer comprises LiCoO2, NaCoO2, LiMnO2 and / or LiMn2O4; The bonding layer comprises nickel oxide; The metal interlayer comprises nickel; and The base layer comprises aluminum, stainless steel, titanium and / or carbon.

31. The electrochemical method according to claim 1, wherein the top oxide layer comprises yttrium oxide (Y₂O₃) stabilized zirconium oxide (ZrO₂); The bonding layer contains Al2O3; The metal interlayer comprises an MCrAlY alloy, where M is Ni and / or Co; and The base layer contains a turbine blade alloy.

32. The electrochemical method of claim 1, wherein the substrate layer comprises a plane.

33. The electrochemical method according to claim 1, wherein the substrate layer comprises a curved surface.

34. The electrochemical method according to claim 1, wherein the substrate layer has a wire shape factor.

35. An adhesive and structurally stable multilayer component, comprising: A bonding layer on a substrate, the bonding layer comprising a binary oxide; and The top oxide layer on the bonding layer, the top oxide layer comprising a ternary oxide.

36. The adhesive and structurally stable multilayer assembly of claim 35, wherein the bonding layer is formed by electrochemical passivation of a metal interlayer on the substrate layer.

37. The adhesive and structurally stable multilayer assembly of claim 35, wherein the bonding layer is free of pinholes or physical gaps, and / or The bonding layer provides full surface coverage of the metal intermediate layer and / or the base layer.

38. The adhesive and structurally stable multilayer component according to claim 35, wherein the binary oxide is selected from: aluminum oxide, nickel oxide, cobalt oxide, manganese oxide, and iron oxide, and / or The binary oxides thereon are transition metal oxides and / or formed from group 13-16 metals (Al, Ga, In, Tl, Nh, Si, Ge, Sn, Pb, Fl, As, Sb, Bi, Mc, Se, Te, Po and / or Lv).

39. The adhesive and structurally stable multilayer assembly of claim 35, wherein the bonding layer has a thickness in the range of 5 nm to 10 μm or 5 nm to 1 μm.

40. The adhesive and structurally stable multilayer assembly of claim 35, wherein the substrate layer comprises a metal and / or conductive material selected from: metals, alloys, conductive polymers, and conductive composite materials.

41. The adhesive and structurally stable multilayer assembly of claim 35, wherein the top oxide layer comprises a ternary oxide.

42. The adhesive and structurally stable multilayer assembly of claim 35, wherein the top oxide layer comprises alkali metal group (Li, Na, K) / alkaline earth metal group (Ca, Mg) intercalated post-transition group / group 13 / lower group 14-15 (Sn, Sb, Pb, Bi) oxides, individually, as a phase mixture, or as doped versions thereof.

43. The adhesive and structurally stable multilayer assembly of claim 35, wherein the top oxide layer comprises a ternary oxide selected from the group consisting of: LiCoO2, NaCoO2, LiMnO2, LiMn2O4, and LiNi. x Mn y Co z O2 and NaNi x Mn y Co z O2, where (x+y+z=1) and 0≤x,y,z≤1.

44. The adhesive and structurally stable multilayer assembly of claim 35, wherein the top oxide layer has a thickness in the range of 5 nm to 2000 μm or 5 μm to 1000 μm.

45. The adhesive and structurally stable multilayer assembly of claim 35, wherein the top oxide layer comprises LiCoO2, NaCoO2, LiMnO2 and / or LiMn2O4; The bonding layer comprises nickel oxide; and The base layer comprises aluminum, stainless steel, titanium and / or carbon.

46. ​​The adhesive and structurally stable multilayer assembly of claim 35, wherein the top oxide layer comprises yttrium oxide (Y₂O₃) stabilized zirconium oxide (ZrO₂); The bonding layer comprises Al2O3; and The base layer contains a turbine blade alloy.

47. The adhesive and structurally stable multilayer assembly of claim 35, wherein the substrate layer comprises a plane.

48. The adhesive and structurally stable multilayer assembly of claim 35, wherein the substrate layer comprises a curved surface.

49. The adhesive and structurally stable multilayer assembly of claim 35, wherein the substrate layer has a wire shape factor.

50. The adhesive and structurally stable multilayer assembly of claim 35, wherein the top oxide layer comprises a cathode material and the base layer comprises a current collector for a lithium-ion or sodium-ion battery.

51. The adhesive and structurally stable multilayer assembly of claim 35, wherein the top oxide layer comprises a thermal barrier coating, an anti-corrosion coating, and / or an oxide-based gas sensor, and wherein the base layer comprises a metal substrate.

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