Method of manufacturing a thin-layer lithiated material
By depositing a thin layer of metal oxide on a substrate and then performing crystallization annealing, the problem of uneven lithiation material layer in the prior art was solved, and a uniform lithiation material layer suitable for three-dimensional batteries was achieved, thereby improving electrochemical performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CENT NAT DE LA RECH SCI (C N R S)
- Filing Date
- 2021-09-30
- Publication Date
- 2026-06-12
AI Technical Summary
Existing technologies cannot manufacture lithiation material layers with uniform thicknesses between 1 nm and 1 μm, especially for positive electrode layers suitable for complex undulating substrates and three-dimensional batteries.
A metal oxide thin layer is deposited on a substrate using atomic layer deposition technology. A lithiation thin layer is formed through multiple purging and diffusion steps, and then crystallization annealing is performed at 600 to 800 °C to form an electrochemically active composite material.
It enables the deposition of uniform lithium-ion material layers on complex undulating substrates, suitable for three-dimensional batteries, and improves electrochemical performance.
Smart Images
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Abstract
Description
[0001] This invention relates to a method for manufacturing lithium-containing materials. More specifically, this invention relates to a method for manufacturing lithium-containing materials deposited in thin layers on a substrate surface.
[0002] In the existing art, methods for forming thin layers of materials on various types of substrates are known, particularly for producing lithium-ion material layers, i.e., lithium-containing material layers. These lithium-ion materials are used especially in batteries, for example, to form electrodes or electrolytic cells, or any other electrical storage devices. These layers can be deposited using precursors via atomic layer deposition (ALD), chemical vapor deposition (ALCVD), or even atomic layer epitaxy (ALE). In particular, ALD is a thin-layer deposition technique that utilizes a gas-surface reaction to expose the surface on which the material layer is desired to be deposited to a variety of continuous chemical precursors.
[0003] However, under the current background technology, there is no method that allows the manufacture of lithium-ion materials containing a film layer, that is, a layer of electrochemically active composite material with a thickness between 1 nm and 1 μm, and which is particularly uniform and can match the complex or uncomplex undulations of the substrate surface on which the lithium-ion material is deposited.
[0004] In the context of this invention, complex undulations refer to a substrate having cavities, tubes, or columns processed therein to form a three-dimensional skeleton with an area-to-volume ratio greater than 10.
[0005] Furthermore, there is no existing background technology that allows for the fabrication of a lithium-based positive electrode layer suitable for three-dimensional or 3D batteries.
[0006] In the context of this invention, a three-dimensional battery or 3D battery is a battery having a pattern defined as having a thickness greater than 5 μm. For example, a three-dimensional battery or 3D battery can be a microcell consisting of at least six layers of material deposited in a suitable manner on a substrate, said substrate being pre-structured to form a three-dimensional pad with a predetermined surface area. These six layers are: an insulating layer, two current collector layers, a negative electrode layer, and a positive electrode layer. The two electrode layers are separated by a solid electrolyte. These six layers may optionally be protected by an additional encapsulation layer to prevent aging of the 3D battery.
[0007] The objective of this invention is, in particular, to overcome all or part of the aforementioned defects.
[0008] Therefore, according to a first aspect, the present invention relates to a method for manufacturing a lithium-ion material on a substrate, the lithium-ion material comprising a plurality of thin layers, and the method comprising the following steps:
[0009] a) Place a substrate made of materials intended for use in batteries in a reaction chamber.
[0010] c1) Through the reaction chamber, a precursor of a first metal, selected from nickel, manganese, cobalt, chromium, lanthanum, niobium, vanadium, iron, titanium, and aluminum, is deposited at least once on at least a portion of the surface of the substrate.
[0011] c2) Purge the reaction chamber at least once.
[0012] c3) The first oxidizing agent is diffused at least once through the reaction chamber to obtain a thin layer of oxide of the first metal.
[0013] c4) Purge the reaction chamber at least once.
[0014] f1) Through the reaction chamber, the lithium precursor is deposited at least once on top of the oxide thin layer of the first metal to form a lithiation thin layer.
[0015] f2) Purge the reaction chamber at least once.
[0016] The method is characterized in that it further includes step g) after step f2): crystallization annealing at a temperature between 600 and 800°C for 1 to 4 hours to obtain a lithiated material.
[0017] In the sense of this invention, a material intended for use in a battery refers to any type of material that has sufficient mechanical strength to withstand mechanical damage from conventional heat treatments performed in the battery manufacturing process, is chemically inert, and is electrochemically stable under temperature influences.
[0018] According to this first aspect of the invention, electrochemically active materials can thus be manufactured, comprising at least one thin layer of oxide of the first metal as described above and a lithiation thin layer on a substrate. Therefore, electrochemically active composite materials can be deposited on the substrate, providing electrochemical performance suitable for three-dimensional batteries. For example, by this manufacturing method, a lithiation material comprising a thin layer can be manufactured, particularly one that is homogeneous on a surface greater than 7.5 cm on one side.
[0019] It should be noted that this type of lithium-ion material can be used, for example, in electrochemical storage devices. In particular, such lithium-ion materials can be used to manufacture two-dimensional or three-dimensional batteries, especially three-dimensional micro-batteries, such as lithium-ion batteries, for a variety of applications. In two-dimensional or three-dimensional batteries, the substrate can be in the form of a two-dimensional or three-dimensional object.
[0020] In the context of this invention, a two-dimensional object refers to a planar object, such as silicon, or any object that can serve as a mechanical substrate for a material layer in the manufacture of two-dimensional batteries.
[0021] In the context of this invention, a three-dimensional object refers to an object covered by stacked deposited material, such as a thin layer of ALD (Alternating Layer Deposition). For example, a three-dimensional object may exhibit a structured appearance on at least one surface, which can be achieved through microelectronic etching techniques or micro / nano object growth techniques.
[0022] Similarly, using the method according to the invention, when the substrate is microstructured, that is, when the substrate has a certain surface roughness on at least one surface, the deposited lithium material matches the shape of such microstructure, so that lithium material that perfectly matches the microstructure of the substrate can be easily formed, thereby obtaining a uniform material with the same thickness on the entire surface on which the material is formed.
[0023] In particular, the specific surface area of a microstructured substrate is larger than that of a planar substrate (i.e., unstructured). For example, the area of the substrate can be increased by arranging microstructures with large aspect ratios on the surface of the substrate. The aspect ratio of a microstructure corresponds, for example, the ratio of its longitudinal dimension to its minimum lateral dimension (e.g., the minimum lateral distance between two microstructures arranged consecutively on the substrate).
[0024] For example, the microstructured substrate can be a substrate containing slice-type, column-type, and channel-type microstructures, or it can be a substrate containing, for example, the microstructures described in disclosure WO2015052412. It should also be noted that the substrate can be fabricated using microfabrication techniques and should be able to withstand thermal processes applied during the implementation of its fabrication method, such as in the deposition and annealing steps.
[0025] For example, the substrate can be selected from silicon, SiO2, Al2O3, titanium, glass, etc. The substrate of the material. In addition, the substrate can be flexible or rigid.
[0026] It should be noted that the precursor of the first metal can exist in liquid or powder form. For example, the precursor of the first metal can be selected from the following precursors: FeCl2, FeCp2, Fe(thd)3, La(thd)3, CoCp2, MnCp2, Mn(thd)3, NiCp2, TiCl4, NbOEt5, Cr(OCI)2, but is not limited to these.
[0027] It should be noted that in step c3), the first oxidizing agent diffuses, allowing the chemical bonds of the elements present on the surface after step c1) to be broken. This first oxidizing agent is selected based on the strength of the chemical bonds of the relevant elements. For example, ozone is preferably used to promote the oxidation of manganese, thus ensuring the formation of MnO2.
[0028] Preferably, the thickness of the first metal oxide layer is between 5 and 15 nm. This first layer can also preferably be deposited at a rate of 0.5 to 1 Å per ALD cycle.
[0029] It should be noted that lithium precursors can exist in powder form. For example, lithium precursors can be LiOtBu, but are not limited to this.
[0030] Preferably, the thickness of the lithiation layer is between 5 and 1000 nm. This first layer can also preferably be deposited at a rate of 0.5 to 1 A per ALD cycle.
[0031] In one specific embodiment, it is advantageous to functionalize the substrate to facilitate subsequent deposition steps, particularly to promote the adhesion of the first few atomic monolayers of the precursor of the first metal to the substrate. This functionalization also allows for a substrate with a surface containing little or no contaminating elements, enabling a surface state favorable to the desired chemical reaction in subsequent deposition steps. Therefore, in this embodiment, the method further includes at least step b1) between steps a) and c1): functionalizing the substrate, wherein step b1) functionalization includes diffusing water through the reaction chamber, and subsequently step b2): purging the water reaction chamber.
[0032] Preferably, the functionalization in step b1) is carried out at a temperature between 180°C and 220°C.
[0033] Preferably, the method further includes a preferred step b3): a first round of repetition, repeating steps b1) and b2) n1 times, wherein step b3) is performed between steps b2) and c1). This step allows for a significant reduction, or even complete elimination, of any contamination that may be present on the substrate surface prior to the implementation of subsequent deposition steps.
[0034] In one specific embodiment, it is advantageous to manufacture a lithiated material comprising at least one thin layer of oxide of a first metal and one thin layer of oxide of a second metal, rather than a single thin layer of oxide of the first metal. In fact, the presence of at least two thin layers of oxides of two different (transition) metals in the lithiated material allows for the acquisition of a lithiated material with higher electrochemical activity compared to those currently used. In particular, such lithiated materials can therefore be used to fabricate the positive electrode of a three-dimensional battery operating at a high potential, i.e., in Li / Li... + It operates at a potential higher than 4V. Therefore, in this embodiment, the method further includes the following steps between c2) and f1):
[0035] -At least step d1): Through the reaction chamber, a precursor of a second metal selected from nickel, manganese, cobalt, chromium, lanthanum, titanium, and aluminum, or a precursor of a phosphate, is deposited on at least a portion of the thin layer of the oxide of the first metal.
[0036] -At least step d2): Purge the reaction chamber.
[0037] -At least step d3): Diffusion of the second oxidizing agent through the reaction chamber to obtain a thin layer of the second metal oxide or phosphate, and
[0038] -At least step d4): purge the reaction chamber at least once.
[0039] Just as in step c3), the diffusion of the first oxidizing agent allows for the diffusion of the second oxidizing agent, which disrupts the chemical bonds of the elements present on the surface after step d1). These two oxidizing agents are chosen based on the strength of the chemical bonds of the relevant elements.
[0040] It should be noted that the first oxidizing agent can be the same as the second oxidizing agent, but this is not mandatory.
[0041] For example, ozone, water, or any other oxygen-containing compound such as CO2 may be mentioned as the first and / or second oxidizing agent. Combinations of oxygen precursors may also be used in the diffusion steps of the oxidizing agents, which may be carried out separately or simultaneously in the same diffusion step of the first or second oxidizing agent.
[0042] Further steps similar to d1) through d4) described above can be performed to obtain additional metal oxide thin layers. For example, the following materials can thus be obtained in this way: Li x M1 y M2 z M3 s O tM1, M2, and M3 are selected from transition metals such as Ni, Mn, Co, Cr, and Al, for example, LiNi. 1 / 3 Mn 1 / 3 Co 1 / 3 O2, Li x Ni y Co z Al t O2 (where y+z+t=1).
[0043] Preferably, the thickness of the oxide layer of the second metal is between 5 and 15 nm. This layer can also preferably be deposited at a rate of 0.5 to 1 Å per ALD cycle.
[0044] It should be noted that the second metal or phosphate precursor can be the same as or different from the one deposited in step c1). Moreover, by forming thin layers from precursors of different transition metals, ternary, quaternary, or pentaneous lithiation materials can be formed.
[0045] It should be noted that the precursor of the second metal can exist in liquid or powder form. For example, the precursor of the second metal or phosphate can be selected from the following precursors: La(thd)3, CoCp2, MnCp2, Mn(thd)3, NiCp2, TiCl4, Cr(OCI)2, but is not limited to these.
[0046] Preferably, the method further includes step c5): a second repetition, repeating steps c1) to c4) n2 times. It should be noted that step c5) is preferably performed between steps c4) and d1). Therefore, uniform growth of the oxide of the first metal can be obtained through these steps c1) to c4), and the final stoichiometry of the desired lithium-ion material can also be controlled.
[0047] Preferably, the method further includes step d5): a third repetition, repeating steps d1) to d4) n3 times, wherein step d5) is performed between steps d4) and d1). Therefore, uniform growth of the oxide of the second metal can be obtained through these steps d1 to d4), and the final stoichiometry of the desired lithium-ion material can also be controlled.
[0048] Preferably, the method further includes step e): a fourth repetition, repeating steps c1) to d4) n4 times. It should be noted that step e) is preferably performed between steps d5) and f1). Therefore, the thickness of each thin layer of the oxides of the first and second metals can be increased, thus increasing the thickness of the active material to improve the performance of three-dimensional batteries containing such lithium-ion materials.
[0049] In one specific embodiment, it is advantageous to significantly reduce or even eliminate the carbonaceous material formed after the atomic layer deposition of the lithium precursor in step f1). Therefore, in this embodiment, the method further includes at least step f3) between steps f2) and g): forced oxidation of the lithiation thin layer, the forced oxidation of step f3) including the diffusion of water in the reaction chamber, and subsequently step f4): purging the reaction chamber.
[0050] Preferably, the forced oxidation in step f3) is carried out at a temperature between 180°C and 220°C.
[0051] In steps b1) and f3), the water is preferably deionized water.
[0052] Preferably, the method further includes step f5): a fifth repetition, repeating steps f1) to f4) n5 times, wherein step f5) is performed between steps f4) and g). Therefore, the thickness of the atomic layer of the lithium precursor can be increased.
[0053] Preferably, n5 is defined as follows: n5 = 0.05 * (n2 + n3) * n4. For example, in this way, the ratio of manganese and nickel in the ALD cycle can be optimized to allow the formation of lithiated materials while limiting the presence of lithium oxide (NiO) and Li2MnO3.
[0054] Moreover, by adjusting the value from n1 to n5, different stoichiometry of materials containing lithium, nickel, manganese and oxygen (hereinafter referred to as LNMO materials) can be obtained.
[0055] Furthermore, it should be noted that the purging step involves blowing an inert gas through the reaction chamber, especially after each precursor injection, or even simultaneously with the precursor injection. As a variation, multiple purging injections can be performed at intervals between precursor injections. The purging step aims to remove all unreacted reagents, thereby ensuring the fabrication of lithium-ion materials based on the self-limiting gas-surface reaction. Furthermore, reaction chamber purging can be performed by circulating the purge gas through the reaction chamber, or, as a variation, by evacuating the reaction chamber by depressurization. Suitable purge gases include inert gases such as nitrogen and argon; however, any suitable gas or gas mixture that does not react with the deposition of a thin layer containing the precursor can be introduced.
[0056] According to a second aspect, the present invention relates to lithium-ion materials that can be obtained by the above-described method.
[0057] The invention will be better understood by reading the following description, given only as an example, and in conjunction with the accompanying drawings, in which:
[0058] [ Figure 1 ] Figure 1An embodiment of the manufacturing method according to the present invention is illustrated schematically;
[0059] [ Figure 2 ] Figure 2 A cross-sectional view of the material of Example 1 before annealing, obtained according to an embodiment of the present invention, is shown, on which an alumina (Al2O3) protective layer is also deposited;
[0060] [ Figure 3 ] Figure 3 A cross-sectional view of the annealed material of Example 1 obtained according to an embodiment of the present invention is shown, on which an alumina (Al2O3) protective layer is also deposited.
[0061] Device / Product
[0062] Device:
[0063] -Reaction chamber: ALD PICOSUN R200 reactor.
[0064] product:
[0065] Substrate: BT Electronics, Siltronix (Si(100), 5-10 ohm.cm, 2"-4", 1 side polished)
[0066] -ALD precursor:
[0067] Platinum: Trimethyl(III)methylcyclopentadienylplatinum(IV), 99%, Merck, STREM Chemical
[0068] _Phosphate: Trimethyl phosphate, minimum 97%, Merck, STREM Chemical
[0069] Lithium: Lithium tert-butoxide, 98%+, Merck, STREM Chemical
[0070] Alumina: Trimethylaluminate, minimum 98%, Merck, STREM Chemical
[0071] Nickel: Bis(cyclopentadiene)nickel, 99% (nickel dicenocene), Merck, STREM Chemical
[0072] Manganese: Tris(2,2,6,6-tetramethyl-3,5-heptanoic acid)manganese(III), 99% Mn(TMHD)3, Merck, STREAM Chemical Example
[0073] Example 1: Manufacturing a first lithiation material according to the present invention
[0074] In this example, the lithium-ion material is LiNi applied to a two-dimensional substrate. 0.5 Mn 1.5 O4 (LNMO) was obtained using ALD atomic layer deposition technology, as shown in the figure below.
[0075] The method followed in this example includes four main steps:
[0076] - Formation of a thin layer of MnO2;
[0077] - Formation of a thin NiO layer;
[0078] - A thin lithiation layer is formed on the surface;
[0079] - Crystallization annealing to allow the formation of LNMO materials.
[0080] More specifically, the sequential steps performed in this example are as follows (e.g.) Figure 1 As shown):
[0081] a) Place the two-dimensional substrate in the reaction chamber;
[0082] b1) Substrate functionalization, including diffusion of deionized water through the reaction chamber heated to 195°C;
[0083] b2) Purge the reaction chamber;
[0084] b3) Repeat the first round, repeating steps b1) and b2) 10 times;
[0085] c1) Mn(thd)s are blown into the reaction chamber at a temperature of 195°C to allow the precursor of manganese (Mn) to undergo atomic layer deposition in order to form a thin layer containing Mn on the substrate surface.
[0086] c2) Purge the reaction chamber;
[0087] c3) Ozone is diffused through a reaction chamber heated to 195°C to promote the reaction of ozone with the Mn-containing thin layer formed on the substrate surface at the end of step c1), thereby forming a MnO2 thin layer.
[0088] c4) Purge the reaction chamber;
[0089] c5) Repeat the second round, repeating steps c1) and c4) 27 times;
[0090] d1) Ni(Cp)2 is blown into a reaction chamber heated to 195°C to allow the nickel (Ni) precursor to undergo atomic layer deposition, thereby forming a nickel-containing thin layer on the surface of the MnO2 thin layer.
[0091] d2) Purge the reaction chamber;
[0092] d3) Ozone is blown through a reaction chamber heated to 195°C to diffuse the ozone and promote the reaction of the ozone with the nickel formed on the surface of the thin layer of MnO2 formed at the end of the previous step d1), thus forming a thin layer of NiO.
[0093] d4) Purge the reaction chamber;
[0094] d5) Repeat the third round, repeating steps d1) to d4) 10 times;
[0095] e) Fourth round of repetition, repeating steps c1) to d4) 52 times: to obtain MnO2-NiO;
[0096] f1) LiOtBu is blown into a reaction chamber heated to approximately 225°C to allow the lithium precursor to undergo atomic layer deposition, thereby forming a lithium-containing thin layer on the surface of the MnO2-NiO layer.
[0097] f2) Purge the reaction chamber;
[0098] f3) Deionized water is diffused through a reaction chamber heated to approximately 225°C to oxidize the lithium oxide thin film, thereby promoting the reaction of water with the lithium-containing layer formed on the surface of the MnO2-NiO layer formed at the end of the previous step f1), thus obtaining a lithium oxide thin film.
[0099] f4) Purge the reaction chamber;
[0100] f5) The fifth repetition, steps f1) to f4) are repeated 96 times;
[0101] g) Crystallize and anneal in air at a temperature of approximately 700°C for 2 hours.
[0102] Through this operation, a LiNi layer with a thickness of 100 nm was obtained deposited on a silicon substrate. 0.5 Mn 1.5 Lithated materials of O4.
[0103] It should be noted that the above steps can also be applied to microstructured substrates, such as the substrate described in document WO2015052412.
[0104] test
[0105] Before performing step g) annealing (see...) Figure 2 ) and afterwards (see Figure 3 Under a transmission electron microscope (usually abbreviated as TEM) (see...), Figure 2 and Figure 3The lithiation material obtained according to Example 1 was analyzed. The lithiation material was deposited on a platinum layer, which was applied using a platinum precursor and served as the current collector layer of the battery. The platinum layer and the entire lithiation material were protected by an 85 nm ALD (alumina oxide) Al2O3 deposition layer to prevent cutting by a focused ion probe (FIB), which was deposited on the lithium oxide layer of the material at 300°C before annealing and was applied using an alumina precursor.
[0106] Material analysis before annealing, such as Figure 2 As shown. Grids A, B, C, and D represent the various superimposed layers mentioned above (as shown in the figure, A and B are based on the first scale, and C and D are based on the second scale). In Figure 2 On squares A and B, from bottom to top, a first alumina layer, a first platinum layer, a manganese-nickel layer, a second alumina layer, and a second platinum layer are observed. Figure 2 On squares C and D, from bottom to top, the first platinum layer, the manganese-nickel layer, and the second aluminum oxide layer can be observed.
[0107] Furthermore, it is important to note that there were no voids between the aforementioned layers prior to annealing. The absence of voids is a characteristic of strong interlayer adhesion. Additionally, no interdiffusion of alumina was observed in squares E to L, nor was interdiffusion observed between platinum and the lithiation material (in this case, a manganese-nickel layer, as the lithium layer is not visible in the photograph, and lithium is invisible under a transmission electron microscope). The platinum layer with the lithiation material applied on top, in the case of a battery, can serve as a current collector layer. Its surface appears rough, and the orientation of its grains affects the orientation of the lithiation material deposited on it, thus the lithiation material acts as a positive electrode layer. A close mixing of manganese and nickel was also observed, forming a homogeneous layer, indicating good elemental distribution during ALD deposition. Therefore, the nickel layer formed after the deposition of the manganese thin layer diffuses into the interior of the manganese layer, forming a manganese-nickel layer.
[0108] Material analysis after annealing, as follows Figure 3 As shown. In Figure 3 On squares A and B, from bottom to top, the first alumina layer, platinum layer, manganese-nickel layer, and second alumina layer are observed. Figure 2 On squares C and D, from bottom to top, a platinum layer, a manganese-nickel layer, and a second alumina layer are observed. Furthermore, the influence of the grain orientation of the current collector layer and the platinum layer on the preferential grain orientation of the LNMO material can be further distinguished here. Generally, demixing exists between manganese and nickel. In fact, nickel-poor regions are observed to be rich in manganese, and vice versa, but in different proportions. It should also be noted that NiO was observed after annealing and the formation of the LNMO material.
[0109] Figure 2 and Figure 3Each square in the diagram corresponds to a chemical mapping of a stacked layer on a silicon substrate. The legend for each square, from E to L, indicates a chemical element. Each chemical element is assigned a color (or grayscale). The analytical technique used also allows for the overlay of colors or grayscale values for various elements (see [link to diagram]). Figure 2 Squares B and C in the middle, and Figure 3 (squares B and D in the text).
[0110] In each of these two figures (2 and 3), there are two different scales (one scale for squares A and B, and the other for squares C and D). On the cell diagram, TEM analysis and chemical mapping of all superimposed elements are shown. Figure 2 The squares E to L and Figure 3 On the grids E to L, each chemical element (Al, Pt, Ni, Mn) is shown individually. This allows for more precise information, such as whether elements diffuse into or out of each other between successive layers, or the distribution of these different elements. Figure 3 Manganese-nickel elements were observed in squares G and H, as well as K and L. Figure 1 The demixing of the manganese-nickel ratio considered in the text can also be observed between the platinum layer and the alumina layer. Figure 3 There is no interdiffusion between the platinum and manganese-nickel layers on the squares F to H or I, K and L.
Claims
1. A method for manufacturing a lithium-ion material on a substrate, the lithium-ion material comprising a plurality of thin layers, and the method comprising the following steps: a) Place a substrate made of materials intended for use in batteries in a reaction chamber. c1) Through the reaction chamber, a precursor of a first metal, selected from nickel, manganese, cobalt, chromium, lanthanum, niobium, vanadium, iron, titanium, and aluminum, is deposited at least once on at least a portion of the surface of the substrate. c2) Purge the reaction chamber at least once. c3) The first oxidizing agent is diffused at least once through the reaction chamber to obtain a thin layer of oxide of the first metal. c4) Purge the reaction chamber at least once. f1) Through the reaction chamber, the lithium precursor is deposited at least once on top of the oxide thin layer of the first metal to form a lithiation thin layer. f2) Purge the reaction chamber at least once. The method is characterized in that it further includes step g) after step f2): crystallization annealing at a temperature between 600°C and 800°C for 1 to 4 hours to obtain a lithiated material.
2. The method of claim 1, further comprising at least step b1) between steps a) and c1): functionalizing the substrate, wherein the functionalization of step b1) includes diffusing water through the reaction chamber, and subsequently performing step b2): purging the reaction chamber.
3. The method according to claim 2, further comprising step b3): a first round of repetition, repeating steps b1) and b2) n1 times, wherein step b3) is performed between steps b2) and c1).
4. The method according to any one of claims 1 to 3, comprising step c5): a second round of repetition, repeating steps c1) to c4) n2 times.
5. The method according to any one of claims 1 to 4, further comprising, between step c2) and f1): -At least step d1): Through the reaction chamber, a precursor of a second metal selected from nickel, manganese, cobalt, chromium, lanthanum, titanium, and aluminum, or a precursor of a phosphate, is deposited on at least a portion of the thin layer of the oxide of the first metal. -At least step d2): Purge the reaction chamber. -At least step d3): Diffusion of the second oxidizing agent through the reaction chamber to obtain a thin layer of the second metal oxide or phosphate, and -At least step d4): purge the reaction chamber at least once.
6. The method according to claim 5, further comprising step d5): a third repetition, repeating steps d1) to d4) n3 times, wherein step d5) is performed between steps d4) and d1).
7. The method according to any one of claims 5 or 6, further comprising step e): a fourth round of repetition, repeating steps c1) to d4)n4 times.
8. The method according to any one of claims 1 to 7, further comprising at least step f3) between steps f2) and g): forced oxidation of the lithiation thin film, wherein the forced oxidation of step f3) includes diffusing water in the reaction chamber, and subsequently performing step f4): purging the reaction chamber.
9. The method according to claim 8, further comprising step f5): a fifth repetition, repeating steps f1) to f4) n5 times, wherein step f5) is performed between steps f4) and g).