Integrated negative electrode with negative electrode protection, preparation method thereof, all-solid-state lithium ion battery and electric device

Abstract

The application provides an integrated negative electrode with negative electrode protection, a preparation method of the integrated negative electrode, a full-solid-state lithium ion battery and an electric device, and relates to the technical field of lithium ion batteries. The integrated negative electrode with negative electrode protection comprises a flexible polymer substrate layer, a fluorinated flexible polymer interface layer, a metal seed layer and a lithium metal layer which are stacked in sequence. The fluorinated flexible polymer interface layer, the metal seed layer and the lithium metal layer jointly form an M / F synergistically functionalized interface structure. During the operation of the full-solid-state battery, the fluorinated flexible polymer interface layer can generate a stable interface layer rich in LiF in situ, and the metal seed layer can promote uniform deposition of lithium and form a Li-M alloy interface, thereby realizing the synergistic effect of nucleation regulation, interface stabilization and mechanical buffering, and significantly improving the cycle stability of the lithium metal negative electrode.

Description

Technical Field

[0001] This invention relates to the field of lithium-ion battery technology, and in particular to an integrated negative electrode with negative electrode protection, its preparation method, an all-solid-state lithium-ion battery, and an electrical device thereof. Background Technology

[0002] Lithium metal anodes have an extremely high theoretical specific capacity (3860 mAh·g). -1 ) and the lowest electrochemical potential ( 3.04 V vs Li / Li + Lithium metal anodes are considered an important anode material for realizing next-generation high-energy-density batteries. However, in practical applications, lithium metal anodes still face serious interface stability problems, such as lithium dendrite growth, instability at the solid electrolyte-anode interface, and continuously increasing interface impedance. These problems can lead to a decrease in battery cycle life and pose potential safety hazards.

[0003] To address these issues, researchers have proposed various artificial SEI construction strategies, including inorganic protective layers, polymer protective layers, composite interface layers, and electrolyte additive regulation. Among these, constructing a fluorine-rich interface layer to promote lithium fluoride (LiF) formation is considered an effective way to improve the stability of the lithium metal interface. LiF possesses high mechanical modulus, excellent chemical stability, and good lithium-ion conductivity, which can effectively suppress lithium dendrite growth and reduce interfacial side reactions.

[0004] However, most current methods for constructing fluorine-rich interfaces primarily utilize fluorinated polymers (such as PVDF and PTFE) or electrolyte additives. These materials typically possess high mechanical modulus and low flexibility, making it difficult to buffer the volume changes of lithium metal during lithium deposition and stripping, which can easily lead to interface layer cracking or failure. Furthermore, some fluorination methods require complex operations on lithium metal directly, placing high demands on environmental conditions and hindering large-scale production.

[0005] Meanwhile, in the preparation of lithium metal thin film anodes, the commonly used lithium metal anodes usually rely on copper (Cu) current collectors as the support structure, which not only increases the overall mass of the battery and reduces the energy density, but also increases the material cost and the difficulty of storage and transportation.

[0006] The main problems with existing lithium metal anode protection technologies are: most existing fluorine-rich interface materials are rigid fluoropolymers, which lack sufficient elasticity and are difficult to buffer the volume changes of lithium metal during charging and discharging. There is a stress concentration problem at the contact interface between lithium metal and solid electrolyte. This problem can easily lead to cracking or failure of the interface layer between the two, resulting in a decline in battery electrical performance.

[0007] Therefore, developing an integrated structure with good flexible buffering capacity, capable of forming a stable fluorine-rich interface layer in situ and suitable for evaporating lithium metal anodes is of great significance for improving the interface stability and energy density of all-solid-state lithium metal batteries.

[0008] In view of this, the present invention is hereby proposed. Summary of the Invention

[0009] The purpose of this invention is to provide an integrated negative electrode with negative electrode protection, its preparation method, an all-solid-state lithium-ion battery, and an electrical device. This invention solves at least the following technical problems: (1) Many artificial SEI construction methods require complex processing on the lithium metal surface, which is difficult to operate and has strict requirements on environmental conditions; (2) Some interface layers are prone to cracking or failure during cycling, making it difficult to maintain a stable lithium-ion transport channel for a long time; (3) Existing single flexible polymers have been widely used as buffer layers in all-solid-state batteries, but their wettability with lithium metal is poor, and they cannot provide effective interface protection; (4) Current lithium metal thin film rolls still rely on Cu current collectors (energy density is limited), and storage and transportation costs are high.

[0010] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted: In a first aspect, the present invention provides an integrated negative electrode with negative electrode protection, wherein the integrated negative electrode with negative electrode protection comprises a flexible polymer substrate layer, a fluorinated flexible polymer interface layer, a metal seed layer and a lithium metal layer stacked sequentially.

[0011] Furthermore, the flexible polymer substrate layer is a polydimethylsiloxane film and / or a polyurethane film, preferably a polydimethylsiloxane film.

[0012] Furthermore, the thickness of the flexible polymer substrate layer is 10~500 μm, preferably 50~200 μm.

[0013] Furthermore, the fluorinated flexible polymer interface layer is a fluorinated polydimethylsiloxane interface layer and / or a fluorinated polyurethane interface layer.

[0014] Furthermore, the thickness of the fluorinated flexible polymer interface layer is 2~20 nm.

[0015] Furthermore, the fluorinated polydimethylsiloxane interface layer comprises a polydimethylsiloxane film and / or a fluorinated polyurethane film with surface-modified fluorinated functional groups; wherein the fluorinated functional groups include any one or a combination of at least two of -CF, -CF2, and -CF3.

[0016] Furthermore, the thickness of the metal seed layer is 5~100 nm, preferably 10~50 nm.

[0017] Furthermore, the grain size of the metal seed layer is 5~50 nm, the porosity of the metal seed layer is 0~20%, the roughness of the metal seed layer is 1~20 nm, and the density of the metal seed layer is 80~100%.

[0018] Furthermore, the thickness of the lithium metal layer is 1~50 μm, preferably 5~20 μm.

[0019] Furthermore, the grain size of the lithium metal layer is 50~1000 nm, the porosity of the lithium metal layer is 0~30%, the roughness of the lithium metal layer is 10~1000 nm, and the density of the lithium metal layer is 70~100%.

[0020] In a second aspect, the present invention provides a method for preparing an integrated negative electrode with negative electrode protection as described in the first aspect, the method comprising: The flexible polymer substrate is subjected to fluorination treatment, magnetron sputtering deposition of a metal seed layer, and evaporation deposition of a lithium metal layer in sequence to obtain the integrated negative electrode with negative electrode protection.

[0021] Furthermore, the process prior to fluorination includes a pretreatment, which includes plasma treatment of the flexible polymer substrate.

[0022] Furthermore, the gas used in the plasma includes any one or a combination of at least two of O2, Ar, air, and O3, preferably O2.

[0023] Furthermore, the process parameters for plasma treatment include: the gas is O2, the gas flow rate is 10~30 sccm, the plasma power is 20~50 W, the reaction chamber pressure is 10~50 Pa, and the treatment time is 30~120 s.

[0024] Furthermore, the pretreatment also includes washing and drying.

[0025] Furthermore, the cleaning process includes: sequentially placing the flexible polymer substrate layer in acetone, ethanol, and water for ultrasonic cleaning.

[0026] Furthermore, the ultrasonic cleaning in acetone, ethanol, and water is performed at frequencies of 40-60 kHz and for times of 5-15 min, respectively.

[0027] Furthermore, the drying process includes drying with nitrogen gas.

[0028] Furthermore, the preprocessing specifically includes the following steps: The flexible polymer substrate is cleaned and dried, and then subjected to oxygen plasma treatment to obtain an activated flexible polymer substrate.

[0029] Furthermore, the fluorination treatment is carried out using a fluorine-containing gas plasma modification method.

[0030] Furthermore, the fluorine-containing gas includes gases that generate fluorine radicals and / or fluorine-containing active species under plasma conditions, preferably fluorinated alkane gases and / or fluorine-containing inorganic gases.

[0031] Furthermore, the process parameters for the fluorination treatment include: gas flow rate of 10~50 sccm, reaction chamber pressure of 10~60 Pa, radio frequency plasma power of 50~200 W, treatment time of 1~10 min, and treatment temperature of 20~30℃.

[0032] Furthermore, the magnetron sputtering equipment is a DC magnetron sputtering system.

[0033] Furthermore, the sputtering target for the magnetron sputtering is a high-purity metal target with a purity of not less than 99.99%.

[0034] Furthermore, the metal includes any one or a combination of at least two of silver, zinc, tin, gold, platinum, and gallium.

[0035] Furthermore, the magnetron sputtering process parameters include: argon as the working gas, a working gas flow rate of 20~40 sccm, a sputtering working gas pressure of 0.3~1.0 Pa, a sputtering power of 30~100 W, a substrate temperature of 20~30℃, and a deposition time of 30 s~10 min.

[0036] Furthermore, the vapor deposition method includes thermal evaporation vapor deposition or electron beam evaporation vapor deposition.

[0037] Furthermore, the evaporation source for the vapor deposition is lithium metal particles and / or lithium blocks with a purity of not less than 99.9%.

[0038] Furthermore, when the vapor deposition method is thermal evaporation vapor deposition, the process parameters of the vapor deposition include: evaporation temperature of 400~600℃, vapor deposition rate of 0.1~1.0 nm / s, substrate temperature of 20~30℃, and deposition time of 10~300 min.

[0039] Furthermore, when the evaporation method is electron beam evaporation, the evaporation process parameters include: electron beam power of 1~5000 W, beam current of 50~200 mA, deposition rate of 1~10 Å / s, substrate temperature of 20~30℃, and deposition time of 10~300 min.

[0040] Thirdly, the present invention provides an all-solid-state lithium-ion battery, the all-solid-state lithium-ion battery comprising an integrated negative electrode with negative electrode protection as described in the first aspect, or an integrated negative electrode with negative electrode protection prepared by the preparation method described in the second aspect.

[0041] Fourthly, the present invention provides an electrical device comprising an all-solid-state lithium-ion battery as described in the third aspect.

[0042] Compared with the prior art, the present invention has the following beneficial effects: (1) The integrated negative electrode with negative electrode protection described in this invention can generate a LiF protective layer in situ at the interface during the lithium deposition process, thereby effectively suppressing lithium dendrite growth and improving interface stability; (2) The integrated negative electrode with negative electrode protection described in this invention has a low elastic modulus and good flexibility. During lithium deposition and stripping, it can effectively buffer the volume change of lithium metal, reduce interface stress concentration and maintain stable interface contact. (3) The integrated negative electrode with negative electrode protection described in this invention can reduce the overpotential for lithium deposition nucleation and form a Li-Ag alloy structure at the interface, thereby inducing uniform lithium deposition and improving the morphology of lithium metal deposition. (4) The integrated negative electrode with negative electrode protection described in this invention forms an organic-inorganic composite interface structure with the formed LiF inorganic protective layer and the flexible polymer substrate, which can simultaneously realize interface mechanical buffering and ion conduction regulation. (5) The integrated negative electrode with negative electrode protection described in this invention does not require traditional copper current collector support, thereby reducing battery weight and increasing overall battery energy density; (6) The preparation process of the integrated negative electrode with negative electrode protection described in this invention is simple and has industrialization potential. The plasma treatment, magnetron sputtering and evaporation processes used are all mature thin film preparation technologies with good process controllability and large-scale production potential. They are suitable for evaporation of lithium metal negative electrodes and all-solid-state battery systems. Attached Figure Description

[0043] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0044] Figure 1 A schematic diagram of the integrated negative electrode with negative electrode protection provided by the present invention.

[0045] Among them, 1 is a flexible polymer substrate layer, 2 is a fluorinated flexible polymer interface layer, 3 is a metal seed layer, and 4 is a lithium metal layer. Detailed Implementation

[0046] Unless otherwise defined herein, the scientific and technical terms used in conjunction with this invention shall have the meanings commonly understood by one of ordinary skill in the art. The meaning and scope of terms shall be clear; however, in any case of potential ambiguity, the definitions provided herein shall prevail over any dictionary or foreign definitions. In this application, unless otherwise stated, the use of "or" means "and / or". Furthermore, the use of the term "comprising" and other forms is non-limiting.

[0047] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0048] In a first aspect, the present invention provides an integrated negative electrode with negative electrode protection, such as... Figure 1 As shown, the integrated negative electrode with negative electrode protection includes a flexible polymer substrate layer 1, a fluorinated flexible polymer interface layer 2, a metal seed layer 3, and a lithium metal layer 4 stacked sequentially.

[0049] It should be noted that, firstly, this invention uses a flexible polymer film as a substrate, buffering volume changes through a flexible interface. This film possesses a low elastic modulus and good flexibility, effectively buffering lithium metal volume changes during lithium deposition and stripping, reducing interfacial stress concentration, and maintaining stable interfacial contact. Secondly, this invention modifies the surface of the flexible polymer film with fluorination, constructing a fluorinated flexible polymer interface layer in situ. This allows for the in-situ generation of a LiF protective layer at the interface during lithium deposition, effectively suppressing lithium dendrite growth and improving interface stability. Next, by setting a metal seed layer, the lithium deposition nucleation overpotential is reduced, and a Li-M alloy structure is formed at the interface, thereby inducing uniform lithium deposition and improving the lithium metal deposition morphology. Finally, a negative electrode containing a self-supporting lithium metal film is constructed, eliminating the need for traditional copper current collectors, thus reducing battery weight and increasing overall battery energy density. Furthermore, the LiF inorganic protective layer formed by the fluorinated flexible polymer interface layer and the flexible polymer substrate form an organic-inorganic composite interface structure, achieving interfacial mechanical buffering and ion conduction regulation.

[0050] As an optional implementation, the flexible polymer substrate is a polydimethylsiloxane (PDMS) film and / or a polyurethane (PU) film.

[0051] In a preferred embodiment, the flexible polymer substrate is a polydimethylsiloxane (PDMS) film.

[0052] It should be noted that polydimethylsiloxane (PDMS) film is used as the flexible substrate material. Due to the excellent chemical stability, mechanical flexibility, and low elastic modulus of PDMS, it can effectively buffer volume changes during lithium metal deposition and peeling, thereby maintaining stable interfacial contact and reducing interfacial stress concentration. At the same time, PDMS has good film-forming properties and processability, making it suitable as a flexible anode support substrate.

[0053] As an optional implementation, the thickness of the flexible polymer substrate layer is 10~500 μm, for example, it can be 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, etc.

[0054] In a preferred embodiment, the thickness of the flexible polymer substrate layer is 50~200 μm.

[0055] As an optional implementation, the fluorinated flexible polymer interface layer is a fluorinated polydimethylsiloxane (PDMS) interface layer and / or a fluorinated polyurethane (PU) interface layer.

[0056] As an optional implementation, the thickness of the fluorinated flexible polymer interface layer is 2~20 nm, for example, it can be 2 nm, 4 nm, 6 nm, 8 nm, 10 nm, 12 nm, 14 nm, 16 nm, 18 nm, 20 nm, etc.

[0057] As an optional implementation, the fluorinated polydimethylsiloxane interface layer includes a polydimethylsiloxane (PDMS) film and / or a fluorinated polyurethane film with surface-modified fluorinated functional groups; wherein the fluorinated functional groups include any one or a combination of at least two of -CF, -CF2, and -CF3.

[0058] In a preferred embodiment, the fluorinated polydimethylsiloxane interface layer comprises a polydimethylsiloxane (PDMS) film with a surface modified with fluorinated functional groups; wherein the fluorinated functional groups include any one or a combination of at least two of -CF, -CF2, and -CF3.

[0059] It should be noted that polydimethylsiloxane (PDMS) film is used as a flexible substrate material, and the surface of the PDMS film is fluorinated and modified by plasma (such as carbon tetrafluoride CF4) to introduce fluorine-containing functional groups such as -CF, -CF2, and -CF3, thereby forming a fluorinated PDMS interface layer. The surface energy of the fluorinated PDMS film increases by 200%. This fluorinated interface layer can provide a fluorine source during subsequent contact with lithium metal. When this interface layer comes into contact with lithium metal, the fluorine-containing functional groups can react with lithium at the interface to generate an inorganic protective layer of lithium fluoride (LiF) in situ at the interface. The formed LiF-enriched interface layer has high mechanical strength and excellent chemical stability, and can effectively suppress lithium dendrite growth and reduce interfacial side reactions.

[0060] As an optional implementation, the metal seed layer is a metal seed layer formed on the surface of the fluorinated flexible polymer interface layer by magnetron sputtering.

[0061] It should be noted that the present invention further deposits a metal (M) nanoseed layer on the surface of the fluorinated PDMS interface layer by magnetron sputtering. The metal M, which has good conductivity and affinity for lithium, is selected so that it can serve as a nucleation site for lithium deposition in the subsequent lithium evaporation deposition process and form a Li-M alloy at the interface. This reduces the overpotential for lithium deposition nucleation and induces uniform lithium deposition, improves the deposition morphology of the lithium metal anode, and is beneficial to the formation of an ultrathin controllable lithium layer.

[0062] As an optional implementation, the thickness of the metal seed layer is 5~100 nm, for example, it can be 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, etc.

[0063] In a preferred embodiment, the thickness of the metal seed layer is 10~50 nm.

[0064] As an optional implementation, the grain size of the metal seed layer is 5~50 nm, for example, it can be 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, etc.; the porosity of the metal seed layer is 0~20%, for example, it can be 0%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, etc.; the roughness of the metal seed layer is 1~20 nm, for example, it can be 1 nm, 2 nm, 4 nm, 6 nm, 8 nm, 10 nm, 12 nm, 14 nm, 16 nm, 18 nm, 20 nm, etc.; and the density of the metal seed layer is 80~100%, for example, it can be 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, 96%, 98%, 100%, etc.

[0065] As an optional implementation, the material of the metal seed layer includes any one or a combination of at least two of silver, zinc, tin, gold, platinum, and gallium.

[0066] In a preferred embodiment, the metal seed layer is made of silver.

[0067] As an optional implementation, the lithium metal layer is a lithium metal layer formed on the surface of the metal seed layer by vacuum evaporation.

[0068] It should be noted that this invention utilizes a vacuum evaporation process to deposit a lithium metal thin film on the surface of a metal seed layer, thereby constructing a multilayer integrated structure consisting of a PDMS flexible substrate, a LiF fluorine-rich interface layer, a Li-M nucleation interface, and a lithium metal layer, forming a continuous and dense lithium metal anode. This structure not only enables the control of lithium deposition morphology and improves interface stability, but also allows for the direct construction of a self-supporting lithium anode structure without the need for traditional copper current collectors, thus reducing battery mass and increasing battery energy density, making it suitable for all-solid-state lithium metal battery systems.

[0069] As an optional implementation, the thickness of the lithium metal layer is 1~50 μm, for example, it can be 1 μm, 2 μm, 4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, etc.

[0070] In a preferred embodiment, the thickness of the lithium metal layer is 5~20 μm.

[0071] As an optional implementation, the grain size of the lithium metal layer is 50~1000 nm, for example, it can be 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm, 1000 nm, etc. The porosity of the lithium metal layer is 0~30%, for example, it can be 0%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, etc. The roughness of the lithium metal layer is 10~1000 nm, for example, it can be 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, etc. The photomasks are 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm, 1000 nm, etc., and the density of the lithium metal layer is 70~100%, for example, it can be 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, 96%, 98%, 100%, etc.

[0072] In a second aspect, the present invention provides a method for preparing an integrated negative electrode with negative electrode protection as described in the first aspect, the method comprising: The flexible polymer substrate is subjected to fluorination treatment, magnetron sputtering deposition of a metal seed layer, and evaporation deposition of a lithium metal layer in sequence to obtain the integrated negative electrode with negative electrode protection.

[0073] It should be noted that the plasma treatment, magnetron sputtering and evaporation processes used are all mature thin film preparation technologies with good process controllability and large-scale production potential, and are suitable for evaporation of lithium metal anodes and all-solid-state battery systems.

[0074] As an optional implementation, the fluorination process further includes a pretreatment, which includes oxygen plasma treatment of the flexible polymer substrate.

[0075] It should be noted that oxygen plasma pretreatment of the flexible polymer substrate can further remove surface organic contaminants, thereby obtaining a clean and activated flexible polymer substrate.

[0076] As an optional implementation, the gas used at the plasma includes any one or a combination of at least two of O2, Ar, air, and O3.

[0077] In a preferred embodiment, the gas used in the plasma is O2.

[0078] It should be noted that the gas used in the plasma treatment of this invention is O2 to increase hydroxyl and carboxyl functional groups, improve surface roughness, and increase active sites. In particular, oxygen plasma pretreatment constructs an active layer rich in polar functional groups on the polymer surface. This improves the grafting efficiency of fluorine during fluorine-containing plasma treatment and regulates the surface energy and interfacial chemical environment. Consequently, it promotes the reaction between Li and the fluorine-containing structure during subsequent lithium evaporation, inducing the formation of a uniform and dense LiF interfacial layer, and achieving controllable construction of the interfacial structure.

[0079] As an optional implementation, the process parameters of the plasma treatment include: the gas is O2; the gas flow rate is 10~30 sccm, for example, 10 sccm, 12 sccm, 14 sccm, 16 sccm, 18 sccm, 20 sccm, 22 sccm, 24 sccm, 26 sccm, 28 sccm, 30 sccm, etc.; the plasma power is 20~50 W, for example, 20 W, 22 W, 24 W, 26 W, 28 W, 30 W, 32 W, 34 W, 36 W, 38 W, 40 W, 42 W, 44 W, 46 W, 48 W, 50 W, etc.; and the reaction chamber pressure is 10~50 Pa, for example, 10 Pa, 12 Pa, 14 Pa, 16 Pa, 18 Pa, 20 Pa, 22 Pa, 24 Pa, 26 Pa, 28 Pa, 30 Pa, 32 Pa, 34 Pa, 36 Pa, etc. Pa, 38 Pa, 40 Pa, 42 Pa, 44 Pa, 46 Pa, 48 Pa, 50 Pa, etc., with a processing time of 30~120 s, for example, 30 s, 40 s, 50 s, 60 s, 70 s, 80 s, 90 s, 100 s, 110 s, 120 s, etc.

[0080] As an optional implementation, the pretreatment also includes washing and drying.

[0081] As an optional implementation, the cleaning includes: ultrasonically cleaning the flexible polymer substrate layer in acetone, ethanol and water in sequence.

[0082] As an optional implementation, the frequency of ultrasonic cleaning in acetone, ethanol and water is independently 40~60 kHz, for example, 40 kHz, 42 kHz, 44 kHz, 46 kHz, 48 kHz, 50 kHz, 52 kHz, 54 kHz, 56 kHz, 58 kHz, 60 kHz, etc.; the time is independently 5~15 min, for example, 5 min, 6 min, 8 min, 10 min, 12 min, 14 min, 15 min, etc.

[0083] As an optional implementation, the cleaning includes: ultrasonically cleaning the PDMS film sequentially in acetone, anhydrous ethanol, and deionized water, wherein the ultrasonic cleaning time with acetone is 5-15 min, preferably 10 min; the ultrasonic cleaning time with anhydrous ethanol is 5-15 min, preferably 10 min; the ultrasonic cleaning time with deionized water is 5-15 min, preferably 10 min; and the ultrasonic frequency is 40-60 kHz.

[0084] As an optional implementation, the drying process includes drying with nitrogen gas.

[0085] As an optional implementation, the preprocessing specifically includes the following steps: The flexible polymer substrate is cleaned and dried, and then subjected to oxygen plasma treatment to obtain an activated flexible polymer substrate.

[0086] As an optional implementation, the preprocessing specifically includes the following steps: The PDMS film was ultrasonically cleaned sequentially in acetone, anhydrous ethanol, and deionized water. The ultrasonic cleaning time was 5-15 min for acetone, 5-15 min for anhydrous ethanol, and 5-15 min for deionized water. The ultrasonic frequency was 40-60 kHz. After cleaning, the film was dried with high-purity nitrogen. Subsequently, the PDMS substrate was pretreated with oxygen plasma. The oxygen plasma treatment conditions were: O2 gas, gas flow rate 10-30 sccm, plasma power 20-50 W, reaction chamber pressure 10-50 Pa, and treatment time 30-120 s, thereby obtaining a clean and activated PDMS substrate.

[0087] As an optional implementation, the fluorination treatment is carried out using a fluorine-containing gas plasma modification method.

[0088] As an optional implementation, the fluorine-containing gas is a gas capable of generating fluorine free radicals or fluorine-containing active species under plasma conditions.

[0089] As an optional implementation, the fluorinated gas includes fluorinated alkanes and / or fluorinated inorganic gases.

[0090] As an optional implementation, the fluorine-containing gas includes any one or a combination of at least two of carbon tetrafluoride (CF4), trifluoromethane (CHF3), hexafluoroethane (C2F6), octafluoropropane (C3F8), and sulfur hexafluoride (SF6).

[0091] As an optional implementation, the process parameters of the fluorination treatment include: a gas flow rate of 10~50 sccm, for example, 10 sccm, 15 sccm, 20 sccm, 25 sccm, 30 sccm, 35 sccm, 40 sccm, 45 sccm, 50 sccm, etc.; a reaction chamber pressure of 10~60 Pa, for example, 10 Pa, 15 Pa, 20 Pa, 25 Pa, 30 Pa, 35 Pa, 40 Pa, 45 Pa, 50 Pa, 55 Pa, 60 Pa, etc.; a radio frequency plasma power of 50~200 W, for example, 50 W, 60 W, 70 W, 80 W, 90 W, 100 W, 110 W, 120 W, 130 W, 140 W, 150 W, 160 W, 170 W, 180 W, 190 W, 200 W, etc.; and a treatment time of 1~10 min, for example, 1 min, 2 min, etc. The processing times are 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, etc., with a processing temperature of 20~30℃, such as 20℃, 22℃, 24℃, 25℃, 26℃, 28℃, 30℃, etc.

[0092] It should be noted that the PDMS substrate is placed in a plasma reaction chamber for surface fluorination treatment, which employs a fluorine-containing gas plasma modification method. Under plasma bombardment, the fluorine-containing gas decomposes to generate F radicals, which react with the PDMS surface, introducing fluorine-containing functional groups such as -CF, -CF2, and -CF3, thereby forming a fluorinated modified layer with a thickness of approximately 2–20 nm. This fluorinated interface layer can provide a fluorine source during subsequent lithium metal deposition, participating in the interfacial reaction in the early stages of lithium deposition and promoting the formation of the LiF inorganic interface. After treatment, the sample is transferred to the next deposition process under an inert argon gas protective environment to avoid contamination from moisture and oxygen in the air.

[0093] As an optional implementation, the fluorination treatment specifically includes the following steps: The pretreated PDMS substrate was placed in a plasma reaction chamber for surface fluorination treatment. The fluorination treatment employed carbon tetrafluoride (CF4) plasma modification, with the CF4 gas purity not less than 99.99%. During the plasma reaction, the CF4 gas flow rate was controlled at 10–50 sccm, the reaction chamber pressure at 10–60 Pa, the radio frequency plasma power at 50–200 W, the treatment time at 1–10 min, and the treatment temperature at room temperature (20–30 °C).

[0094] As an optional implementation, the magnetron sputtering device is a DC magnetron sputtering system.

[0095] As an optional implementation, the sputtering target for magnetron sputtering is a high-purity metal target with a purity of not less than 99.99%.

[0096] As an optional implementation, the metal includes any one or a combination of at least two of silver, zinc, tin, gold, platinum, and gallium.

[0097] As an optional implementation, the magnetron sputtering process parameters include: argon as the working gas, a working gas flow rate of 20~40 sccm (e.g., 20 sccm, 22 sccm, 24 sccm, 26 sccm, 28 sccm, 30 sccm, 32 sccm, 34 sccm, 36 sccm, 38 sccm, 40 sccm, etc.), a sputtering working gas pressure of 0.3~1.0 Pa (e.g., 0.3 Pa, 0.4 Pa, 0.5 Pa, 0.6 Pa, 0.7 Pa, 0.8 Pa, 0.9 Pa, 1.0 Pa, etc.), and a sputtering power of 30~100 W (e.g., 30 W, 40 W, 50 W, 60 W, 70 W, 80 W, 90 W, 100 W, etc.). W, etc., with a substrate temperature of 20~30℃, such as 20℃, 22℃, 24℃, 25℃, 26℃, 28℃, 30℃, etc., and a deposition time of 30 s~10 min, such as 30 s, 40 s, 50 s, 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, etc.

[0098] It should be noted that the fluorinated PDMS substrate is placed in a magnetron sputtering deposition apparatus, and an Ag seed layer is deposited on its surface by magnetron sputtering. By controlling the deposition time, the thickness of the deposited Ag seed layer is 5~100 nm, preferably 10~50 nm. The Ag seed layer can serve as a nucleation site for lithium deposition during the subsequent lithium metal deposition process, improving the uniformity of lithium deposition at the interface, and forming a Li-Ag alloy interface with lithium during the deposition process, thereby reducing the overpotential for lithium deposition nucleation.

[0099] As an optional implementation, the magnetron sputtering specifically includes the following steps: A fluorinated PDMS substrate was placed in a magnetron sputtering deposition apparatus, and an Ag seed layer was deposited on its surface by magnetron sputtering. The magnetron sputtering apparatus was a DC magnetron sputtering system, and the sputtering target used was a high-purity silver target with a purity of not less than 99.99%. During the deposition process, the deposition chamber was first evacuated to a substrate vacuum level ≤ 5 × 10⁻⁶. -4 The sputtering pressure is controlled at 0.3-1.0 Pa, and then high-purity argon gas is introduced as the working gas, with the argon gas flow rate controlled at 20-40 sccm. The sputtering working gas pressure is controlled at 30-100 W, and the substrate temperature is maintained at room temperature (20-30℃). By controlling the deposition time within the range of 30 s-10 min, the thickness of the deposited Ag seed layer is 5-100 nm, preferably 10-50 nm.

[0100] As an optional implementation, the vapor deposition method includes thermal evaporation vapor deposition or electron beam evaporation vapor deposition.

[0101] As an optional implementation, the evaporation source for the vapor deposition is lithium metal particles and / or lithium blocks with a purity of not less than 99.9%.

[0102] As an optional implementation, when the vapor deposition method is thermal evaporation vapor deposition, the process parameters of the vapor deposition include: an evaporation temperature of 400~600℃, for example, 400℃, 420℃, 440℃, 460℃, 480℃, 500℃, 520℃, 540℃, 560℃, 580℃, 600℃, etc.; a vapor deposition rate of 0.1~1.0 nm / s, for example, 0.1 nm / s, 0.2 nm / s, 0.3 nm / s, 0.4 nm / s, 0.5 nm / s, 0.6 nm / s, 0.8 nm / s, 1.0 nm / s, etc.; a substrate temperature of 20~30℃, for example, 20℃, 22℃, 24℃, 25℃, 26℃, 28℃, 30℃, etc.; and a deposition time of 10~300 min, for example, 10 min, 50 min, 100 min, 150 min, 200 min, etc. min, 250 min, 300 min, etc.

[0103] As an optional implementation, when the evaporation method is electron beam evaporation, the evaporation process parameters include: an electron beam power of 1~5000 W, for example, 1 W, 10 W, 20 W, 40 W, 60 W, 80 W, 100 W, 150 W, 200 W, 250 W, 300 W, 350 W, 400 W, 450 W, 500 W, 600 W, 800 W, 1000 W, 1200 W, 1500 W, 2000 W, 2500 W, 3000 W, 3500 W, 4000 W, 4500 W, 5000 W, etc.; a beam current of 50~200 mA, for example, 50 mA, 60 mA, 80 mA, 100 mA, 120 mA, 140 mA, 160 mA, 180 mA, 200 mA, etc.; and a deposition rate of 1~10. The Å / s value can be, for example, 1 Å / s, 2 Å / s, 3 Å / s, 4 Å / s, 5 Å / s, 6 Å / s, 7 Å / s, 8 Å / s, 9 Å / s, 10 Å / s, etc. The substrate temperature is 20~30℃, for example, 20℃, 22℃, 24℃, 25℃, 26℃, 28℃, 30℃, etc. The deposition time is 10~300 min, for example, 10 min, 50 min, 100 min, 150 min, 200 min, 250 min, 300 min, etc.

[0104] It should be noted that during the lithium deposition process, lithium first undergoes uniform nucleation on the Ag seed layer to form a continuous and dense lithium metal film. At the same time, the fluorine element in the fluorinated PDMS interface layer participates in the interface reaction in the early stage of lithium deposition, generating an inorganic interface layer rich in LiF in situ at the interface. Finally, a multi-layer structure of Li metal layer / Li-Ag alloy interface / LiF-PDMS interface layer / PDMS substrate is formed, thereby constructing an integrated lithium metal anode structure.

[0105] As an optional implementation, the vapor deposition specifically includes the following steps: The sample is transferred to a vacuum evaporation coating system for lithium metal deposition. The deposition method can be thermal evaporation or electron beam evaporation, with the evaporation source being high-purity lithium metal particles or lithium blocks with a purity of not less than 99.9%. During the deposition process, the deposition chamber is first evacuated to a high vacuum state, ensuring the substrate vacuum level reaches ≤5×10⁻⁶. -5 Pa, and then the lithium metal is evaporated and deposited on the substrate surface by heating the evaporation source. The evaporation temperature is controlled at 400~600℃, the evaporation rate is controlled at 0.1-1.0nm / s, and the substrate temperature is maintained at room temperature of 20~30℃. The thickness of the deposited lithium metal film is 1~50 μm, preferably 5~20 μm, by adjusting the evaporation time.

[0106] Thirdly, the present invention provides an all-solid-state lithium-ion battery, the all-solid-state lithium-ion battery comprising an integrated negative electrode with negative electrode protection as described in the first aspect, or an integrated negative electrode with negative electrode protection prepared by the preparation method described in the second aspect.

[0107] As an optional implementation, the all-solid-state lithium-ion battery includes: the integrated negative electrode, positive electrode, and solid electrolyte with negative electrode protection.

[0108] As an optional implementation, the solid electrolyte can be any one or a combination of at least two of oxide solid electrolytes, sulfide solid electrolytes, and polymer solid electrolytes.

[0109] As an optional implementation, the oxide solid electrolyte includes LLZO or LAGP.

[0110] As an optional implementation, the sulfide solid electrolyte includes Li 10 GeP2S 12 Or Li6PS5Cl.

[0111] As an optional implementation, the polymer solid electrolyte includes a PEO-LiTFSI system or a PVDF-HFP system.

[0112] As an optional implementation, the assembly steps of the all-solid-state lithium-ion battery include: assembling the battery in an inert atmosphere glove box, wherein the glove box environment is an argon protective atmosphere, wherein the H2O content is less than 0.1 ppm and the O2 content is less than 0.1 ppm, and assembling the integrated negative electrode with negative electrode protection, the solid electrolyte, and the positive electrode. This forms an all-solid-state lithium metal battery.

[0113] As an optional implementation, the assembly method includes a tablet stack structure, a button cell structure, or a pouch cell structure.

[0114] It should be noted that the Ag / F synergistic interface constructed by this method can form a stable LiF-LiAg composite interface layer during battery cycling, thereby effectively reducing interface impedance and suppressing lithium dendrite growth, and improving the cycling stability and safety of lithium metal anode.

[0115] Fourthly, the present invention provides an electrical device comprising an all-solid-state lithium-ion battery as described in the third aspect.

[0116] 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.

[0117] Example 1 This embodiment provides an integrated negative electrode with negative electrode protection, which is prepared by the following steps: S1, PDMS substrate preparation: A 100 μm thick commercial PDMS film (purchased from Dow, formerly Dow Corning SYLGARD™ 184) was selected as a flexible substrate and cut to a size of 2 cm × 2 cm. The PDMS film was then subjected to surface cleaning treatment, sequentially ultrasonically cleaned in acetone, anhydrous ethanol, and deionized water. The ultrasonic cleaning time for each solvent was 10 min, and the ultrasonic frequency was 40 kHz. After cleaning, the film was dried with high-purity nitrogen gas and then pretreated in an oxygen plasma device with an oxygen flow rate of 20 sccm, a plasma power of 30 W, a reaction chamber pressure of 20 Pa, and a treatment time of 60 s to remove residual surface contaminants and activate the PDMS surface.

[0118] S2, PDMS surface fluorination treatment: The S1-treated PDMS substrate was placed in an RF plasma reactor for surface fluorination. The reaction gas was carbon tetrafluoride (CF4) with a purity of 99.99%, a flow rate of 30 sccm, a reaction chamber pressure of 30 Pa, an RF plasma power of 100 W, a treatment time of 5 min, and a treatment temperature of room temperature. This treatment formed a Si-F layer containing -CF, -CF2, and -CF3 atoms on the PDMS surface. x The fluorinated layer of CHF and CHF2 functional groups has a thickness of approximately 10 nm.

[0119] S3, Ag seed layer magnetron sputtering deposition: The S2-fluorinated PDMS substrate was transferred to a DC magnetron sputtering apparatus for Ag seed layer deposition; first, the deposition chamber was evacuated to 5 × 10⁻⁶. -4 Below Pa, high-purity argon gas is introduced as the sputtering gas at a flow rate of 30 sccm and a sputtering working pressure of 0.5 Pa. An Ag target with a purity of 99.99% is selected, and deposition is performed at a sputtering power of 60 W for 3 min, thereby forming an Ag seed layer with a thickness of approximately 20 nm on the fluorinated PDMS surface. The silver seed layer has a grain size of 20 nm, a porosity of 10%, a roughness of 5 nm, and a density of 90%.

[0120] S4, Lithium metal vapor deposition: The sample obtained in S3 was transferred to a vacuum evaporation coating system for lithium metal deposition; the evaporation source was lithium metal particles with a purity of 99.9%, and the chamber was evaporated to 5 × 10⁻⁶ m³ / s before deposition. -5 In a high vacuum environment below Pa, lithium metal is evaporated and deposited by heating an evaporation source at an evaporation temperature of approximately 450°C. The evaporation rate is controlled at 0.5 nm / s, the substrate is kept at room temperature, and the evaporation time is controlled at 335 min to achieve a lithium deposition thickness of approximately 10 μm, thereby forming a continuous and dense lithium metal film on the Ag seed layer. The lithium metal film has a grain size of 300 nm, a porosity of 20%, a roughness of 100 nm, and a density of 80%.

[0121] Example 2 This embodiment provides an integrated negative electrode with negative electrode protection, which is prepared by the following steps: S1, PDMS substrate preparation: A 50 μm thick commercial PDMS film (WACKER ELASTOSIL® RT 601) was selected as the flexible substrate and cut into 2 cm × 2 cm dimensions. Subsequently, the PDMS film underwent surface cleaning treatment by ultrasonically cleaning it in acetone, anhydrous ethanol, and deionized water in sequence. The ultrasonic cleaning time for each solvent was 10 min, and the ultrasonic frequency was 50 kHz. After cleaning, it was dried with high-purity nitrogen gas and then placed in an oxygen plasma device for pretreatment. The oxygen flow rate was 10 sccm, the plasma power was 20 W, the reaction chamber pressure was 10 Pa, and the treatment time was 120 s to remove residual contaminants on the surface and activate the PDMS surface.

[0122] S2, PDMS surface fluorination treatment: The S1-treated PDMS substrate was placed in an RF plasma reaction apparatus for surface fluorination. The reaction gas was carbon tetrafluoride (CF4) with a purity of 99.99% and a flow rate of 10 sccm. The reaction chamber pressure was 10 Pa, the RF plasma power was 50 W, the treatment time was 15 min, and the treatment temperature was room temperature. This treatment formed a fluorinated layer containing functional groups such as -CF, -CF2, and -CF3 on the PDMS surface, with a thickness of approximately 2 nm.

[0123] S3, Ag seed layer magnetron sputtering deposition: The S2-fluorinated PDMS substrate was transferred to a DC magnetron sputtering apparatus for Ag seed layer deposition; first, the deposition chamber was evacuated to 5 × 10⁻⁶. -4Below Pa, high-purity argon gas is introduced as the sputtering gas at a flow rate of 20 sccm and a sputtering working pressure of 0.3 Pa. An Ag target with a purity of 99.99% is selected, and deposition is performed at a sputtering power of 30 W for 6 min, thereby forming an Ag seed layer with a thickness of approximately 10 nm on the fluorinated PDMS surface. The silver seed layer has a grain size of 10 nm, a porosity of 20%, a roughness of 10 nm, and a density of 80%.

[0124] S4, Lithium metal vapor deposition: The sample obtained in S3 was transferred to a vacuum evaporation coating system for lithium metal evaporation. The evaporation source was lithium metal particles with a purity of 99.9%. Before evaporation, the chamber was evaporated to a high vacuum environment below 5 × 10⁻⁵ Pa. The lithium metal was evaporated and deposited by heating the evaporation source at an evaporation temperature of approximately 450 °C. The evaporation rate was controlled at 0.5 nm / s, and the substrate was kept at room temperature. By controlling the evaporation time to 335 min, the lithium deposition thickness was approximately 10 μm, thereby forming a continuous and dense lithium metal film on the Ag seed layer. The lithium metal film had a grain size of 300 nm, a porosity of 20%, a roughness of 100 nm, and a density of 80%.

[0125] Example 3 This embodiment provides an integrated negative electrode with negative electrode protection. The only difference from Embodiment 1 is that the S4 lithium metal evaporation process uses an electron beam evaporation process, specifically: The evaporation process parameters include: an electron beam power of 2000 W, a beam current of 100 mA, a deposition rate of 5 Å / s, a substrate temperature of 30 ℃, and a deposition time of 335 min; resulting in a lithium deposition thickness of approximately 10 μm, thereby forming a continuous and dense lithium metal film on the Ag seed layer; wherein the lithium metal film has a grain size of 300 nm, a porosity of 20%, a roughness of 100 nm, and a density of 80%.

[0126] Example 4 This embodiment provides an integrated negative electrode with negative electrode protection. The only difference from Embodiment 1 is that in the PDMS substrate preparation process of S1, only the surface of the PDMS film is cleaned. The PDMS film is placed in acetone, anhydrous ethanol and deionized water for ultrasonic cleaning in sequence. The ultrasonic cleaning time of each solvent is increased to 30 min, but oxygen plasma treatment is no longer used. Other steps are the same as in Embodiment 1.

[0127] Example 5 This embodiment provides an integrated negative electrode with negative electrode protection. The only difference from Embodiment 1 is that in the surface fluorination treatment of S2, the parameters are adjusted to: gas flow rate 5 sccm, plasma power 60 W, reaction chamber pressure 5 Pa, and treatment time 150 s. The other steps are the same as in Embodiment 1.

[0128] Example 6 This embodiment provides an integrated negative electrode with negative electrode protection. The only difference from Embodiment 1 is that in the surface fluorination treatment of S2, the parameters are adjusted to: gas flow rate 35 sccm, plasma power 15 W, reaction chamber pressure 55 Pa, and treatment time 20 s. The other steps are the same as in Embodiment 1.

[0129] Example 7 This embodiment provides an integrated negative electrode with negative electrode protection. The only difference from Embodiment 1 is that in the Ag seed layer magnetron sputtering deposition in S3, the parameters are adjusted to: argon flow rate 15 sccm, sputtering working pressure 0.2 Pa, sputtering power 120 W, and deposition time 12 min. The other steps are the same as in Embodiment 1.

[0130] Example 8 This embodiment provides an integrated negative electrode with negative electrode protection. The only difference from Embodiment 1 is that in the Ag seed layer magnetron sputtering deposition in S3, the parameters are adjusted to: argon flow rate 45 sccm, sputtering working pressure 1.2 Pa, sputtering power 20 W, and deposition time 20 s. The other steps are the same as in Embodiment 1.

[0131] Comparative Example 1 This comparative example provides a negative electrode, which differs from Example 1 only in that the PDMS surface fluorination treatment in S2 is no longer performed; the other steps are the same as in Example 1.

[0132] Comparative Example 2 This comparative example provides a negative electrode, which differs from Example 1 only in that the Ag seed layer magnetron sputtering deposition in S3 is no longer performed; the other steps are the same as in Example 1.

[0133] Comparative Example 3 This comparative example provides a negative electrode, which differs from Example 1 only in that the polydimethylsiloxane film is replaced with a polyethylene terephthalate film of the same thickness, while the other steps are the same as in Example 1.

[0134] Test case Test samples: integrated negative electrode with negative electrode protection provided in Examples 1-8, and negative electrode provided in Comparative Examples 1-3.

[0135] Battery assembly method: Battery assembly is carried out in an inert atmosphere glove box. The glove box environment is an argon protective atmosphere, in which the H2O content is less than 0.1 ppm and the O2 content is less than 0.1 ppm. The negative electrode, solid electrolyte, and positive electrode materials of the above samples are assembled separately to form an all-solid-state lithium metal battery. The solid electrolyte is specifically LLZO. The positive electrode material is LFP. The assembly method is a coin cell.

[0136] Test method: Electrochemical workstation, electrochemical impedance spectroscopy.

[0137] The specific test results are shown in Table 1: Table 1

[0138] As shown in Table 1, the fluorinated PDMS interface layer, Ag seed layer, and evaporated lithium metal layer together constitute the Ag / F synergistic functionalized interface structure. During the operation of the all-solid-state battery, the fluorinated PDMS interface layer can generate a stable interface layer rich in LiF in situ, while the Ag seed layer can promote uniform lithium deposition and form a Li-Ag alloy interface, thereby achieving a synergistic effect of nucleation regulation, interface stabilization, and mechanical buffering, significantly improving the cycle stability of the lithium metal anode.

[0139] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. An integrated negative electrode with negative electrode protection, characterized in that, The integrated negative electrode with negative electrode protection comprises a flexible polymer substrate layer, a fluorinated flexible polymer interface layer, a metal seed layer, and a lithium metal layer stacked sequentially.

2. The integrated negative electrode with negative electrode protection according to claim 1, characterized in that, The flexible polymer substrate layer includes a polydimethylsiloxane film and / or a polyurethane film, preferably a polydimethylsiloxane film; Preferably, the thickness of the flexible polymer substrate layer is 10~500 μm, more preferably 50~200 μm; Preferably, the fluorinated flexible polymer interface layer is a fluorinated polydimethylsiloxane interface layer and / or a fluorinated polyurethane interface layer. Preferably, the thickness of the fluorinated flexible polymer interface layer is 2~20 nm; Preferably, the fluorinated polydimethylsiloxane interface layer comprises a polydimethylsiloxane film and / or a fluorinated polyurethane film with surface-modified fluorinated functional groups; wherein the fluorinated functional groups include any one or a combination of at least two of -CF, -CF2, and -CF3.

3. The integrated negative electrode with negative electrode protection according to claim 1, characterized in that, The thickness of the metal seed layer is 5~100 nm, preferably 10~50 nm; Preferably, the grain size of the metal seed layer is 5~50 nm, the porosity of the metal seed layer is 0~20%, the roughness of the metal seed layer is 1~20 nm, and the density of the metal seed layer is 80~100%. Preferably, the material of the metal seed layer includes any one or a combination of at least two of silver, zinc, tin, gold, platinum, and gallium; Preferably, the thickness of the lithium metal layer is 1~50 μm, more preferably 5~20 μm; Preferably, the lithium metal layer has a grain size of 50-1000 nm, a porosity of 0-30%, a roughness of 10-1000 nm, and a density of 70-100%.

4. A method for preparing an integrated negative electrode with negative electrode protection according to any one of claims 1 to 3, characterized in that, The preparation method includes: The flexible polymer substrate is subjected to fluorination treatment, magnetron sputtering deposition of a metal seed layer, and evaporation deposition of a lithium metal layer in sequence to obtain the integrated negative electrode with negative electrode protection.

5. The method for preparing an integrated negative electrode with negative electrode protection according to claim 4, characterized in that, The fluorination process includes a pretreatment, which includes plasma treatment of the flexible polymer substrate layer. Preferably, the gas used in the plasma includes any one or a combination of at least two of O2, Ar, air, and O3, with O2 being the most preferred. Preferably, the process parameters for plasma treatment include: the gas is O2, the gas flow rate is 10~30 sccm, the plasma power is 20~50 W, the reaction chamber pressure is 10~50 Pa, and the treatment time is 30~120 s.

6. The method for preparing an integrated negative electrode with negative electrode protection according to claim 4, characterized in that, The fluorination treatment is carried out using a fluorine-containing gas plasma modification method; Preferably, the fluorine-containing gas includes a gas that generates fluorine radicals and / or fluorine-containing reactive species under plasma conditions; Preferably, the process parameters for the fluorination treatment include: a gas flow rate of 10~50 sccm, a reaction chamber pressure of 10~60 Pa, a radio frequency plasma power of 50~200 W, a treatment time of 1~10 min, and a treatment temperature of 20~30℃.

7. The method for preparing an integrated negative electrode with negative electrode protection according to claim 4, characterized in that, The magnetron sputtering equipment is a magnetron sputtering system; Preferably, the sputtering target for magnetron sputtering is a high-purity metal target with a purity of not less than 99.99%; wherein the metal includes any one or a combination of at least two of silver, zinc, tin, gold, platinum, and gallium; Preferably, the magnetron sputtering process parameters include: argon as the working gas, a working gas flow rate of 20~40 sccm, a sputtering working gas pressure of 0.3~1.0 Pa, a sputtering power of 30~100 W, a substrate temperature of 20~30℃, and a deposition time of 30 s~10 min.

8. The method for preparing an integrated negative electrode with negative electrode protection according to claim 4, characterized in that, The vapor deposition method includes thermal evaporation vapor deposition or electron beam evaporation vapor deposition; Preferably, the evaporation source for the vapor deposition is lithium metal particles and / or lithium blocks with a purity of not less than 99.9%; Preferably, when the vapor deposition method is thermal evaporation vapor deposition, the process parameters of the vapor deposition include: evaporation temperature of 400~600℃, vapor deposition rate of 0.1~1.0 nm / s, substrate temperature of 20~30℃, and deposition time of 10~300 min; Preferably, when the evaporation method is electron beam evaporation, the evaporation process parameters include: electron beam power of 1~5000 W, beam current of 50~200 mA, deposition rate of 1~10 Å / s, substrate temperature of 20~30℃, and deposition time of 10~300 min.

9. A fully solid-state lithium-ion battery, characterized in that, The all-solid-state lithium-ion battery includes an integrated negative electrode with negative electrode protection as described in any one of claims 1 to 3, or an integrated negative electrode with negative electrode protection prepared by the preparation method as described in any one of claims 4 to 8.

10. An electrical device, characterized in that, The electrical device includes the all-solid-state lithium-ion battery as described in claim 9.

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