Recycling and reuse methods applicable to failed all-solid-state thin-film lithium batteries

Abstract

This invention provides a method for recycling and reusing failed all-solid-state thin-film lithium batteries. By removing the metal or lithium alloy and its derivatives from the battery surface, an unfailed positive electrode, or an unfailed positive electrode and solid electrolyte membrane, can be obtained, thus achieving the recycling of the all-solid-state thin-film lithium battery. Then, new materials are directly deposited on the recycled battery materials to re-prepare a working all-solid-state thin-film lithium battery. This recycling and reuse method solves the problem of resource waste caused by the current failure of all-solid-state thin-film lithium batteries due to the failure of metallic lithium or lithium alloy negative electrodes. Furthermore, based on the recycled battery materials, all-solid-state thin-film lithium batteries with good electrochemical performance can be re-prepared.

Description

Technical Field

[0001] This invention relates to the field of solid-state battery technology, and more specifically to a method for recycling and reusing failed all-solid-state thin-film lithium batteries. Background Technology

[0002] In the upcoming era of the Internet of Things (IoT), miniaturized electronic devices (such as micro-sensors, microelectromechanical systems, and micro-robots) will wirelessly connect to the internet to enable information interaction and transmission, creating an urgent need for miniature power supplies that match these microelectronic devices. All-solid-state thin-film lithium batteries, with their advantages of small size, integrability, long cycle life, high safety, and low self-discharge rate, are considered ideal power sources for microelectronic devices.

[0003] All-solid-state thin-film lithium batteries are typically prepared by vacuum deposition of a metal current collector, a positive electrode film, an electrolyte film, a negative electrode film, and a negative electrode current collector sequentially on a substrate. Among these, the negative electrode film most commonly uses metallic lithium or lithium alloys. Although they have the lowest potential and high specific capacity, their relatively active chemical properties can easily lead to battery failure during preparation and use, including: (1) When preparing metallic lithium or lithium alloy films on the electrolyte film using the most common thermal evaporation, the electrolyte film is easily directly broken down, leading to a short circuit between the positive and negative electrodes and failure; (2) All-solid-state thin-film lithium batteries using metallic lithium or lithium alloys are prone to failure during transfer, packaging, and storage due to the absorption of air or unfavorable gases (such as carbon dioxide, water vapor, oxygen, and nitrogen) in the glove box; (3) All-solid-state thin-film lithium batteries using metallic lithium or lithium alloys fail during use due to uneven stripping, deposition, or oxidation of lithium, or due to a short circuit between lithium and the positive electrode current collector during use.

[0004] Currently, failed all-solid-state thin-film lithium batteries are generally disposed of as waste, without corresponding recycling methods or means, resulting in a significant waste of resources. Therefore, there is an urgent need to develop a recycling and reuse method suitable for failed all-solid-state thin-film lithium batteries. Summary of the Invention

[0005] The purpose of this invention is to provide a method for recycling and reusing failed all-solid-state thin-film lithium batteries, which solves the problem of waste of resources caused by the failure of all-solid-state thin-film lithium batteries due to the failure of metallic lithium or lithium alloy anodes. Furthermore, based on the recycled battery materials, all-solid-state thin-film lithium batteries with good electrochemical performance can be prepared again.

[0006] According to the purpose of this invention, a method for recycling and reusing failed all-solid-state thin-film lithium batteries is provided, comprising the following steps:

[0007] After removing the encapsulation from the failed all-solid-state thin-film lithium battery, it is immersed in a solvent to dissolve the negative electrode material on the top layer of the failed all-solid-state thin-film lithium battery in the solvent. After cleaning and drying, the recycled battery material is obtained.

[0008] By sequentially adding deposited materials to the recycled battery materials, a new all-solid-state thin-film lithium battery is obtained.

[0009] Preferably, the solvent is an anhydrous organic solvent.

[0010] Preferably, the anhydrous organic solvent is anhydrous ethanol, anhydrous methanol, a mixed solution of organic acid and anhydrous ethanol, or a mixed solution of organic acid and anhydrous methanol.

[0011] Preferably, the mass ratio of organic acid to anhydrous ethanol is (0-0.1):1, and the mass ratio of organic acid to anhydrous methanol is (0-0.1):1; wherein the organic acid is one or more of citric acid, malic acid, tartaric acid, acetic acid, succinic acid, and oxalic acid.

[0012] Preferably, the specific conditions for dissolving the negative electrode material of the top layer of the failed all-solid-state thin-film lithium battery in the solvent are: the solvent temperature is 0℃~200℃, and the immersion time in the solvent is 1min~24h.

[0013] Preferably, during the process of replenishing the deposited material on the recycled battery material, when the failed all-solid-state thin-film lithium battery fails due to a short circuit, a solid electrolyte film is first deposited on the recycled battery material, followed by a negative electrode film, and then a negative current collector is deposited on the negative electrode film; when the failed all-solid-state thin-film lithium battery fails without a short circuit, a negative electrode film is directly deposited on the recycled battery material, followed by a negative current collector.

[0014] Preferably, the anode thin film material for supplementary deposition includes lithium metal, lithium alloy, TiO2, Nb2O5, Si, and SiO2. x SiN x Sn, SnO2, SnN x MnO x NiO, FeO x WO x One or more of them.

[0015] Preferably, the solid electrolyte film to be deposited is Li3PO4, LiPON, Li2SiO3, LiSiON, LiSiPO, LiSiPON, or Li7La3Zr2O. 12 Li3BO4, Li3O X X is one or more of F, Cl, Br, and LiTi(PO4)3.

[0016] Preferably, a thin-film deposition method is used to sequentially deposit new all-solid-state thin-film lithium batteries on the recycled battery materials.

[0017] Preferably, the thin film deposition method includes at least one of magnetron sputtering, pulsed laser deposition, chemical vapor deposition, electron beam evaporation, and thermal evaporation.

[0018] The beneficial effects of this invention are as follows:

[0019] 1. The present invention provides a method for recycling and reusing failed all-solid-state thin-film lithium batteries. The method utilizes a mixture of anhydrous organic solvent and organic acid to impregnate and remove failed metallic lithium or lithium alloy negative electrodes. The lithium metal or lithium alloy can react and dissolve effectively with the anhydrous organic solvent, while the anhydrous environment ensures that the electrolyte is not damaged. Thus, the failed metallic lithium or lithium alloy and its derivatives on the surface of the battery can be effectively removed, and an unfailed positive electrode, or an unfailed positive electrode and a solid electrolyte membrane, can be obtained for further reuse.

[0020] The method of this invention can, on the one hand, promote the reuse of resources and avoid pollution and waste of waste batteries, and on the other hand, reconstruct a working all-solid-state thin-film lithium battery based on the recycled battery materials to obtain better electrochemical performance.

[0021] 2. The recycling method of the present invention can successfully prepare a working all-solid-state thin-film lithium battery with good electrochemical performance, consistent with the characteristic charge-discharge platform of the original failed battery, and has good charge-discharge reversibility and good cycle performance. It can be directly used in practical work and has high promotion and application value. Attached Figure Description

[0022] Figure 1 This is a flowchart of a method for recycling and reusing failed all-solid-state thin-film lithium batteries according to the present invention.

[0023] Figure 2 These are typical photographs of the battery in each step of Example 1.

[0024] Figure 3 The charge-discharge curves of the all-solid-state thin-film lithium battery obtained by recycling in Example 1 are shown.

[0025] Figure 4 The cycling performance diagram shows the all-solid-state thin-film lithium-ion battery obtained by recycling and reuse in Example 1.

[0026] Figure 5 These are typical photographs of the battery in each step of Example 2.

[0027] Figure 6The charge-discharge curve of the all-solid-state thin-film lithium-ion battery obtained by recycling in Example 2.

[0028] Figure 7 The charge-discharge curve of the all-solid-state thin-film lithium battery obtained by recycling in Example 3. Detailed Implementation

[0029] To better understand the technical content of the present invention, specific embodiments are described below in conjunction with the accompanying drawings.

[0030] Various aspects of the invention are described in this disclosure with reference to the accompanying drawings, in which numerous illustrative embodiments are shown. The embodiments of this disclosure are not necessarily intended to encompass all aspects of the invention. It should be understood that the various concepts and embodiments described above, as well as those described below in more detail, can be implemented in any of a number of ways.

[0031] The challenge in recycling failed all-solid-state thin-film lithium batteries lies in the difficulty of simply and efficiently removing the failed metallic lithium or lithium alloy and its derivative layers while ensuring that the electrolyte and cathode materials are not damaged.

[0032] For example, because lithium metal or lithium alloys are in atomic contact with the electrolyte at the interface and the thin-film battery is very thin (<50μm), physically scraping off the failed negative electrode can easily scrape off both the electrolyte and the positive electrode layer at the same time, causing damage to both the electrolyte and the positive electrode layer. Also, because the electrolyte layer is sensitive to moisture (for example, LiPON electrolytes will absorb water and fail when exposed to the atmosphere for a long time), ordinary solvent immersion methods for removing the failed negative electrode can also cause electrolyte failure. Furthermore, using heating methods to bring lithium metal or lithium alloys to their melting point before removing the failed negative electrode can easily cause thermal decomposition of the electrolyte, leading to failure, and can also easily cause oxidation of the negative electrode, making it difficult to remove.

[0033] In view of this, the present invention provides a method for recycling and reusing failed all-solid-state thin-film lithium batteries. By removing the metal or lithium alloy and its derivatives from the surface of the battery, an unfailed positive electrode, or an unfailed positive electrode and a solid electrolyte membrane, can be obtained, thereby realizing the recycling of the all-solid-state thin-film lithium battery. Then, new materials are directly deposited on the recycled battery materials to re-prepare a working all-solid-state thin-film lithium battery.

[0034] Combination Figure 1 In an exemplary embodiment, a method for recycling and reusing failed all-solid-state thin-film lithium batteries is provided, comprising the following steps:

[0035] After removing the encapsulation from the failed all-solid-state thin-film lithium battery, it is immersed in a solvent to dissolve the negative electrode material on the top layer of the failed all-solid-state thin-film lithium battery in the solvent. After cleaning and drying, the recycled battery material is obtained.

[0036] By sequentially adding deposited materials to the recycled battery materials, a new all-solid-state thin-film lithium battery is obtained.

[0037] It should be understood that the negative electrode material of the top layer of the failed all-solid-state thin-film lithium battery is metallic lithium or lithium alloy and its derivatives, such as lithium indium alloy, lithium tin alloy, lithium boron alloy, etc.

[0038] The recovered battery materials include a solid electrolyte film, a positive electrode, and a positive electrode current collector. The negative electrode current collector automatically detaches as the negative electrode dissolves.

[0039] In a preferred embodiment, the solvent is an anhydrous organic solvent.

[0040] In a more preferred embodiment, the anhydrous organic solvent is anhydrous ethanol, anhydrous methanol, a mixed solution of an organic acid and anhydrous ethanol, or a mixed solution of an organic acid and anhydrous methanol.

[0041] In a preferred embodiment, the mass ratio of organic acid to anhydrous ethanol is (0-0.1):1, and the mass ratio of organic acid to anhydrous methanol is (0-0.1):1; wherein the organic acid is one or more of citric acid, malic acid, tartaric acid, acetic acid, succinic acid, and oxalic acid.

[0042] In a preferred embodiment, the specific conditions for dissolving the negative electrode material of the top layer of the failed all-solid-state thin-film lithium battery in a solvent are: the solvent temperature is 0℃~200℃, and the immersion time in the solvent is 1min~24h.

[0043] In a preferred embodiment, during the process of replenishing the deposited material on the recovered battery material, when the failed all-solid-state thin-film lithium battery fails due to a short circuit, a solid electrolyte film is first deposited on the recovered battery material, followed by a negative electrode film, and then a negative current collector is deposited on the negative electrode film; when the failed all-solid-state thin-film lithium battery fails without a short circuit, a negative electrode film is directly deposited on the recovered battery material, followed by a negative current collector.

[0044] The material selected for the negative electrode current collector is a commonly used material in this field, and will not be described in detail here.

[0045] In a more preferred embodiment, the additional deposited negative electrode thin film material includes metallic lithium, lithium alloy (e.g., lithium-indium alloy), TiO2, Nb2O5, Si, and SiO2. x SiN x Sn, SnO2, SnN x MnO x NiO, FeO x WO x One or more of them.

[0046] In a more preferred embodiment, the additionally deposited solid electrolyte film is Li3PO4, LiPON, Li2SiO3, LiSiON, LiSiPO, LiSiPON, or Li7La3Zr2O. 12 Li3BO4, Li3O X X is one or more of F, Cl, Br, and LiTi(PO4)3.

[0047] It should be understood that the supplementary deposited negative electrode material and solid electrolyte material include, but are not limited to, these. When supplementing, the same material as the original failed all-solid-state thin-film battery can be selected, or new materials can be selected according to actual needs.

[0048] In a preferred embodiment, a thin-film deposition method is used to sequentially deposit on the recycled battery material to obtain a new all-solid-state thin-film lithium battery.

[0049] In another preferred embodiment, the thin film deposition method includes at least one of magnetron sputtering, pulsed laser deposition, chemical vapor deposition, electron beam evaporation, and thermal evaporation, which can be selected according to the actual situation.

[0050] In a typical implementation, the failed all-solid-state thin-film lithium battery is a Ti / Pt / LiCoO2 / LiPON / Li / Cu battery deposited on a glass substrate. The failed battery is immersed in a solution of oxalic acid and anhydrous ethanol and left at room temperature for 2 minutes, wherein the mass ratio of oxalic acid to anhydrous ethanol is (0-0.1):1. Then, the surface of the battery is wiped with a lint-free cloth and dried with nitrogen to obtain the recovered failed all-solid-state thin-film lithium battery.

[0051] Next, based on the cause of failure, it is determined whether a solid electrolyte film needs to be deposited first. When the failed all-solid-state thin-film lithium battery failed due to a short circuit, a solid electrolyte film is first deposited on the recovered battery material using magnetron sputtering. For example, LiPON is selected as the solid electrolyte film, with Li3PO4 as the target material and nitrogen as the working gas. The process parameters for magnetron sputtering include: the chamber vacuum degree of magnetron sputtering is less than or equal to 1×10⁻⁶. -4 Pa; and / or, RF sputtering power of 2-6 W / cm² 2 ; and / or, the target-substrate distance is 40-120 mm; and / or, the sputtering time is 1-30 h.

[0052] Typical, but not limiting, chamber vacuum levels for magnetron sputtering are, for example, 5 × 10⁻⁵ Pa or 1 × 10⁻⁴ Pa; typical, but not limiting, RF sputtering power for magnetron sputtering is, for example, 2 W / cm². 2 4W / cm 2 6W / cm 2Typical but not limited target-substrate distances for magnetron sputtering are, for example, 40 mm, 60 mm, 80 mm, 100 mm, and 120 mm; typical but not limited sputtering times for magnetron sputtering are, for example, 1 h, 5 h, 10 h, 20 h, and 30 h.

[0053] When a failed all-solid-state thin-film lithium battery fails due to a non-short circuit, a negative electrode film is directly deposited on the recovered battery material using magnetron sputtering. A negative electrode current collector is then deposited on top of this film. For example, Nb₂O₅ is used as the negative electrode, with an Nb₂O₅ target and argon and oxygen as the working gases. The magnetron sputtering process parameters include: a chamber vacuum of less than or equal to 1 × 10⁻⁴ Pa; and / or a substrate temperature of 25-300℃; and / or an RF or DC sputtering power of 2-6 W / cm². 2 ; and / or, the target-substrate distance is 40-120 mm; and / or, the sputtering time is 1-10 h.

[0054] Typical, but not limiting, chamber vacuum levels for magnetron sputtering are, for example, 5 × 10⁻⁶. -5 Pa, 1×10 -4 Pa; typical but not limiting substrate temperatures for magnetron sputtering are, for example, 25°C, 100°C, and 300°C; typical but not limiting RF sputtering power for magnetron sputtering is, for example, 2 W / cm². 2 4W / cm 2 6W / cm 2 Typical but non-limiting target-substrate distances for magnetron sputtering are, for example, 40 mm, 60 mm, 80 mm, 100 mm, and 120 mm; typical but non-limiting sputtering times for magnetron sputtering are, for example, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, and 10 h.

[0055] In another exemplary embodiment, an all-solid-state thin-film lithium battery is provided, which is prepared by the aforementioned recycling and reuse method applicable to failed all-solid-state thin-film lithium batteries, including the aforementioned recycled substrate, current collector, positive electrode film, electrolyte and supplementally deposited solid electrolyte film, negative electrode film and negative electrode current collector, or including the aforementioned recycled substrate, current collector, positive electrode film, electrolyte, solid electrolyte film and supplementally deposited negative electrode film and negative electrode current collector.

[0056] This invention utilizes a mixture of anhydrous organic solvent and organic acid to impregnate and remove failed metallic lithium or lithium alloy anodes. Lithium metal or lithium alloys react effectively with the anhydrous organic solvent to dissolve and remove them (e.g., lithium reacts with anhydrous ethanol to form liquid lithium ethoxide). Derivatives of lithium metal or lithium alloys can react with organic acids to remove them (e.g., lithium carbonate reacts with oxalic acid to form lithium oxalate, which dissolves in the solvent). The anhydrous environment ensures that the electrolyte remains undamaged. Therefore, this invention can effectively remove failed metallic lithium or lithium alloys and their derivatives from the battery surface, thereby obtaining an undamaged cathode, or an undamaged cathode and solid electrolyte membrane, enabling further reuse.

[0057] The present invention will be further illustrated by the following examples. Unless otherwise specified, the materials in the examples are prepared according to existing methods or purchased directly from the market.

[0058]

Example 1

[0059] (1) Remove the packaging from the glass substrate / Ti / Pt / LiCoO2 / LiPON / Li / Cu all-solid-state thin-film lithium battery that has failed due to oxidation of the lithium metal anode film, then immerse it in a solution with a mass ratio of 0.05 of oxalic acid and anhydrous ethanol, place it at room temperature for 2 minutes, then wipe the surface of the battery with a lint-free cloth, and blow it dry with nitrogen to obtain the recovered Ti / Pt / LiCoO2 / LiPON battery component.

[0060] (2) Based on the recovered battery components, a LiPON solid electrolyte film is prepared on the LiPON using magnetron sputtering. The specific process is as follows:

[0061] After installing the Li3PO4 target and the recovered battery components, close the sputtering chamber and evacuate it to a vacuum of 1.0 × 10⁻⁶. -4 Below Pa, nitrogen gas at 90 sccm was introduced, and the RF sputtering power was set to 2.3 W / cm. 2 With a target-substrate distance of 100 mm, sputtering was performed at room temperature for 3 hours to prepare a LiPON thin film on the original film.

[0062] (3) Based on the above LiPON electrolyte, a lithium metal anode thin film is prepared by thermal evaporation, and then a Cu anode current collector is prepared by magnetron sputtering to obtain a new all-solid-state thin-film lithium battery. The specific process is as follows:

[0063] After installing the lithium metal evaporation source and the aforementioned battery components, close the thermal evaporation chamber and evacuate the chamber to a vacuum level of 1.0 × 10⁻⁶. -4 Below Pa, a 2 μm thick lithium metal anode film was thermally evaporated and deposited. The battery was then transferred to a magnetron sputtering chamber, and after installing the Cu target and the battery components, the sputtering chamber was closed and evacuated to 1.0 × 10⁻⁶.-4 Below Pa, argon gas at 60 sccm is introduced, and the DC sputtering power is set to 1 W / cm. 2 With a target-substrate distance of 100 mm, sputtering for 10 min at room temperature yields a Cu negative electrode current collector, resulting in a fully recyclable aluminum oxide substrate / Ti / Pt / LiCoO2 / LiPON / Li / Cu all-solid-state thin-film lithium battery.

[0064] Figure 2 These are comparative photographs of the failed battery, the recycled battery, and the reused battery in this embodiment. As can be seen from the figures, the method of this invention effectively removes the oxidized and failed lithium anode from the surface of the failed battery to obtain a recycled battery, and enables the reprocessing and reuse of the battery.

[0065] Figure 3 The all-solid-state thin-film lithium battery recycled in this embodiment is stored in a glove box at 30 μA cm⁻¹. -2 The charge-discharge curves for the first two cycles were measured at the specified current. It can be seen that the battery exhibits a clear charge-discharge plateau of 3.9V within the 3-4.2V voltage range, consistent with the characteristic charge-discharge plateau of lithium cobalt oxide. Furthermore, the battery demonstrates good charge-discharge reversibility, with a discharge capacity of 0.28mAh.

[0066] Figure 4 This is a cycle performance diagram of the all-solid-state thin-film lithium battery recycled and reused in this embodiment. It can be seen that the battery achieves a cycle performance of 200 μA cm⁻¹ at room temperature. -2 When charged and discharged at the specified current, the capacity retention rate is still 88.7% after 100 cycles, indicating that the recycled all-solid-state thin-film lithium battery has good cycle performance.

[0067]

Example 2

[0068] (1) Remove the packaging from the aluminum oxide substrate / Ti / Pt / LiCoO2 / LiPON / Li / Cu all-solid-state thin-film lithium battery that has failed due to the oxidation of the lithium metal anode thin film, then immerse it in a solution with a mass ratio of 0.01 of oxalic acid and anhydrous ethanol, place it at room temperature for 2 minutes, then wipe the surface of the battery with a lint-free cloth, and blow it dry with nitrogen to obtain the recovered Ti / Pt / LiCoO2 / LiPON battery component.

[0069] (2) Based on the recovered battery components, Nb₂O₅ anode thin film was prepared by magnetron sputtering, and then Cu anode current collector was prepared by magnetron sputtering to obtain a new all-solid-state thin-film lithium battery. The specific process is as follows:

[0070] After installing the Nb metal target and the aforementioned battery components, close the magnetron sputtering chamber and evacuate the chamber to a vacuum level of 1.0 × 10⁻⁶. -4Below Pa, argon gas at 60 sccm and oxygen gas at 10 sccm are introduced, and the DC sputtering power is set to 1 W / cm. 2 With a target-substrate distance of 100 mm, sputtering was performed at room temperature for 3 hours to prepare the Nb₂O₅ anode. The battery was then transferred to a magnetron sputtering chamber, and after installing the Cu target and the battery components, the sputtering chamber was closed and evacuated to a vacuum of 1.0 × 10⁻⁶. -4 Below Pa, argon gas at 60 sccm is introduced, and the DC sputtering power is set to 1 W / cm. 2 With a target-substrate distance of 100 mm, sputtering for 10 min at room temperature yields a Cu negative electrode current collector, resulting in a fully recyclable aluminum oxide substrate / Ti / Pt / LiCoO2 / LiPON / Nb2O5 / Cu all-solid-state thin-film lithium battery.

[0071] Figure 5 These are comparative photographs of the failed battery, the recycled battery, and the reused battery in this embodiment. It can be seen that by implementing the method of this invention, the oxidized and failed lithium anode on the surface of the failed battery can be effectively removed to obtain a recycled battery, and the battery can be re-prepared and reused.

[0072] Figure 6 The all-solid-state thin-film lithium battery recycled in this embodiment is stored in a glove box at 10 μA cm⁻¹. -2 The charge-discharge curves for the first two cycles, measured at a given current, show that the battery exhibits a distinct charge-discharge plateau of 2.4V within the 0.5-3.2V voltage range. This plateau is consistent with the difference between the characteristic charge-discharge plateau of LiCoO2 (3.9V) and Nb2O5 (1.5V). Furthermore, the battery demonstrates good charge-discharge reversibility, with a discharge capacity of 0.062mAh, indicating that the recyclable all-solid-state thin-film lithium battery can function normally.

[0073]

Example 3

[0074] (1) The alumina substrate / Ti / Pt / Li that has failed due to oxidation of the lithium metal anode film. x The MnO2 / LiPON / Li / Cu all-solid-state thin-film lithium battery was removed from its packaging and then immersed in a solution of oxalic acid and anhydrous ethanol at a mass ratio of 0.01. The solution was left at room temperature for 2 minutes, then the battery surface was wiped with a lint-free cloth and dried with nitrogen to obtain the recovered Ti / Pt / Li. x MnO2 / LiPON battery components.

[0075] (2) Based on the recovered battery components, a lithium metal anode thin film is prepared by thermal evaporation, and then a Cu anode current collector is prepared by magnetron sputtering to obtain a new all-solid-state thin-film lithium battery. The specific process is as follows:

[0076] After installing the lithium metal evaporation source and the aforementioned battery components, close the thermal evaporation chamber and evacuate the chamber to a vacuum level of 1.0 × 10⁻⁶. -4 Below Pa, a 2 μm thick lithium metal anode film was thermally evaporated and deposited. The battery was then transferred to a magnetron sputtering chamber, and after installing the Cu target and the battery components, the sputtering chamber was closed and evacuated to 1.0 × 10⁻⁶. -4 Below Pa, argon gas at 60 sccm is introduced, and the DC sputtering power is set to 1 W / cm. 2 With a target-substrate distance of 100 mm, sputtering at room temperature for 10 min yields a Cu negative electrode current collector, resulting in the final recyclable alumina substrate / Ti / Pt / Li. x MnO2 / LiPON / Li / Cu all-solid-state thin-film lithium battery.

[0077] Figure 7 The all-solid-state thin-film lithium battery recycled in this embodiment is stored in a glove box at 10 μA cm⁻¹. -2 The charge-discharge curves of the first two cycles measured under the current show that the battery has good charge-discharge reversibility and a discharge capacity of 0.0185mAh, indicating that the recycled all-solid-state thin-film lithium battery can work normally.

[0078]

Example 4

[0079] (1) Remove the packaging from the aluminum oxide substrate / Ti / Pt / LiCoO2 / LiSiON / Li / Cu all-solid-state thin film lithium battery that failed due to short circuit between the lithium metal anode film and the cathode, then immerse it in anhydrous ethanol solution, place it at room temperature for 2 minutes, then wipe the battery surface with a lint-free cloth, and blow it dry with nitrogen to obtain the recovered Ti / Pt / LiCoO2 / LiSiON battery component.

[0080] (2) Based on the recovered battery components, a LiSiON solid electrolyte film is prepared on LiSiON using magnetron sputtering. The specific process is as follows:

[0081] After installing the Li2SiO3 target and the recovered battery components, close the sputtering chamber and evacuate it to a vacuum of 1.0 × 10⁻⁶. -4 Below Pa, nitrogen gas at 90 sccm was introduced, and the RF sputtering power was set to 2.3 W / cm. 2 With a target-substrate distance of 100 mm, sputtering was performed at room temperature for 3 hours to prepare a LiSiON thin film on the original film.

[0082] (3) Based on the recovered battery components, a lithium metal anode thin film is prepared by thermal evaporation, and then a Cu anode current collector is prepared by magnetron sputtering to obtain a new all-solid-state thin-film lithium battery. The specific process is as follows:

[0083] After installing the lithium metal evaporation source and the aforementioned battery components, close the thermal evaporation chamber and evacuate the chamber to a vacuum level of 1.0 × 10⁻⁶. -4 Below Pa, a 2 μm thick lithium metal anode film was thermally evaporated and deposited. The battery was then transferred to a magnetron sputtering chamber, and after installing the Cu target and the battery components, the sputtering chamber was closed and evacuated to 1.0 × 10⁻⁶. -4 Below Pa, argon gas at 60 sccm is introduced, and the DC sputtering power is set to 1 W / cm. 2 With a target-substrate distance of 100 mm, sputtering for 10 min at room temperature yields a Cu negative electrode current collector, resulting in a fully recyclable aluminum oxide substrate / Ti / Pt / LiCoO2 / LiSiON / Li / Cu all-solid-state thin-film lithium battery.

[0084]

Example 5

[0085] (1) Remove the packaging from the aluminum oxide substrate / Ti / Pt / LiMn2O4 / LiSiPON / Li / Cu all-solid-state thin-film lithium battery that failed due to a short circuit between the lithium metal anode film and the cathode, then immerse it in anhydrous ethanol solution and place it at room temperature for 2 minutes. Then wipe the surface of the battery with a lint-free cloth and dry it with nitrogen to obtain the recovered Ti / Pt / LiMn2O4 / LiSiPON battery component.

[0086] (2) Based on the recovered battery components, a LiSiPON solid electrolyte film is prepared on LiSiPON using magnetron sputtering. The specific process is as follows:

[0087] After installing the Li-Si-PO target and the recovered battery components, close the sputtering chamber and evacuate it to a vacuum of 1.0 × 10⁻⁶. -4 Below Pa, nitrogen gas at 90 sccm was introduced, and the RF sputtering power was set to 2.3 W / cm. 2 With a target-substrate distance of 100 mm, sputtering was performed at room temperature for 3 hours to prepare a LiSiPON thin film on the original film.

[0088] (3) Based on the recovered battery components, a lithium metal anode thin film is prepared by thermal evaporation, and then a Cu anode current collector is prepared by magnetron sputtering to obtain a new all-solid-state thin-film lithium battery. The specific process is as follows:

[0089] After installing the lithium metal evaporation source and the aforementioned battery components, close the thermal evaporation chamber and evacuate the chamber to a vacuum level of 1.0 × 10⁻⁶.-4 Below Pa, a 2 μm thick lithium metal anode film was thermally evaporated and deposited. The battery was then transferred to a magnetron sputtering chamber, and after installing the Cu target and the battery components, the sputtering chamber was closed and evacuated to 1.0 × 10⁻⁶. -4 Below Pa, argon gas at 60 sccm is introduced, and the DC sputtering power is set to 1 W / cm. 2 With a target-substrate distance of 100 mm, sputtering for 10 min at room temperature yields a Cu negative electrode current collector, resulting in a fully recyclable aluminum oxide substrate / Ti / Pt / LiMn2O4 / LiSiPON / Li / Cu all-solid-state thin-film lithium battery.

[0090]

Example 6

[0091] (1) Remove the packaging from the aluminum oxide substrate / Ti / Pt / MoO3 / LiSiON / Li / Cu all-solid-state thin film lithium battery that failed due to short circuit between the lithium metal anode film and the cathode, then immerse it in anhydrous methanol solution and place it at room temperature for 2 minutes. Then wipe the surface of the battery with a lint-free cloth and blow it dry with nitrogen to obtain the recovered Ti / Pt / MoO3 / LiSiON battery component.

[0092] (2) Based on the recovered battery components, a LiSiON solid electrolyte film is prepared on LiSiON using magnetron sputtering. The specific process is as follows:

[0093] After installing the Li2SiO3 target and the recovered battery components, close the sputtering chamber and evacuate it to a vacuum of 1.0 × 10⁻⁶. -4 Below Pa, nitrogen gas at 90 sccm was introduced, and the RF sputtering power was set to 2.3 W / cm. 2 With a target-substrate distance of 100 mm, sputtering was performed at room temperature for 3 hours to prepare a LiSiON thin film on the original film.

[0094] (3) Based on the recovered battery components, a TiO2 anode thin film was prepared by magnetron sputtering, and then a Cu anode current collector was prepared by magnetron sputtering to obtain a new all-solid-state thin-film lithium battery. The specific process is as follows:

[0095] After installing the TiO2 target and the aforementioned battery components, close the thermal evaporation chamber and evacuate the chamber to a vacuum level of 1.0 × 10⁻⁶. -4 Below Pa, argon gas at 60 sccm and oxygen gas at 10 sccm are introduced, and the RF sputtering power is set to 1 W / cm. 2 With a target-substrate distance of 100 mm, sputtering was performed at room temperature for 10 h to prepare the TiO2 anode. The battery was then transferred to a magnetron sputtering chamber, and after installing the Cu target and the battery components, the sputtering chamber was closed and evacuated to a vacuum of 1.0 × 10⁻⁶.-4 Below Pa, argon gas at 60 sccm is introduced, and the DC sputtering power is set to 1 W / cm. 2 With a target-substrate distance of 100 mm, sputtering for 10 min at room temperature yields a Cu negative electrode current collector, resulting in a fully recyclable aluminum oxide substrate / Ti / Pt / MoO3 / LiSiON / Nb2O5 / Cu all-solid-state thin-film lithium battery.

[0096] While the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the invention. Those skilled in the art can make various modifications and refinements without departing from the spirit and scope of the invention. Therefore, the scope of protection of the present invention shall be determined by the claims.

Claims

1. A method for recycling and reusing failed all-solid-state thin-film lithium batteries, characterized in that, Includes the following steps: After removing the encapsulation from the failed all-solid-state thin-film lithium battery, it is immersed in a solvent to dissolve the negative electrode material on the top layer of the failed all-solid-state thin-film lithium battery in the solvent. After cleaning and drying, the recycled battery material is obtained. A new all-solid-state thin-film lithium battery is obtained by sequentially depositing materials on the recycled battery materials. During the process of replenishing the deposited materials on the recycled battery materials, when the failed all-solid-state thin-film lithium battery fails due to a short circuit, a solid electrolyte film is deposited first on the recycled battery materials, followed by a negative electrode film, and then a negative current collector is deposited on the negative electrode film. When the failed all-solid-state thin-film lithium battery fails without a short circuit, a negative electrode film is directly deposited on the recycled battery materials, and then a negative current collector is deposited on the negative electrode film.

2. The method for recycling and reusing failed all-solid-state thin-film lithium batteries according to claim 1, characterized in that, The solvent is an anhydrous organic solvent.

3. The method for recycling and reusing failed all-solid-state thin-film lithium batteries according to claim 2, characterized in that, The anhydrous organic solvent is anhydrous ethanol, anhydrous methanol, a mixed solution of organic acid and anhydrous ethanol, or a mixed solution of organic acid and anhydrous methanol.

4. The method for recycling and reusing failed all-solid-state thin-film lithium batteries according to claim 3, characterized in that, The mass ratio of organic acid to anhydrous ethanol is (0~0.1):1, and the mass ratio of organic acid to anhydrous methanol is (0~0.1):1; wherein, the organic acid is one or more of citric acid, malic acid, tartaric acid, acetic acid, succinic acid, and oxalic acid.

5. The method for recycling and reusing failed all-solid-state thin-film lithium batteries according to any one of claims 1-4, characterized in that, The specific conditions for dissolving the negative electrode material of the top layer of a failed all-solid-state thin-film lithium battery in a solvent are: solvent temperature of 0℃~200℃, and immersion time in the solvent of 1 min~24 h.

6. The method for recycling and reusing failed all-solid-state thin-film lithium batteries according to claim 1, characterized in that, The anode thin film materials used for supplementary deposition include lithium metal, lithium alloy, TiO2, Nb2O5, Si, and SiO2. x SiN x Sn, SnO2, SnN x MnO x NiO, FeO x WO x One or more of them.

7. The method for recycling and reusing failed all-solid-state thin-film lithium batteries according to claim 1, characterized in that, The supplementary deposited solid electrolyte films are Li3PO4, LiPON, Li2SiO3, LiSiON, LiSiPO, LiSiPON, and Li7La3Zr2O. 12 Li3BO4, Li3OX, where X is one or more of F, Cl or Br, LiTi(PO4)3.

8. The method for recycling and reusing failed all-solid-state thin-film lithium batteries according to claim 1, characterized in that, A new all-solid-state thin-film lithium battery was obtained by sequentially depositing on the recycled battery material using a thin-film deposition method.

9. The method for recycling and reusing failed all-solid-state thin-film lithium batteries according to claim 8, characterized in that, The thin film deposition method includes at least one of magnetron sputtering, pulsed laser deposition, chemical vapor deposition, electron beam evaporation, and thermal evaporation.

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