All-solid-state thin-film lithium battery and preparation method thereof

Abstract

The present invention provides an all-solid-state thin-film lithium battery and a preparation method thereof. The solid-state lithium-ion battery comprises a halide solid electrolyte layer; the halide solid electrolyte layer is formed by magnetron sputtering, which is beneficial to improving the rate performance of the all-solid-state thin-film lithium battery.

Description

Technical Field

[0001] The present invention relates to the technical field of solid-state batteries, and in particular to an all-solid-state thin-film lithium battery and a preparation method thereof. Background Art

[0002] Compared with traditional rigid batteries, which are mostly stacked and assembled, and are very "rigid" in size and shape, flexible batteries have attracted widespread attention because they can withstand deformations such as bending, stretching, twisting, and even folding without changing performance. The development of thin and light flexible lithium-ion batteries with bending stability has become one of the frontiers of research in the field of energy storage. However, most existing all-solid-state thin-film lithium batteries use LIPON as a lithium-ion transmission medium, and the lithium-ion transmission capacity cannot meet higher requirements. Summary of the invention

[0003] Based on this, the present application provides an all-solid-state thin-film lithium battery and a preparation method, which prepares a thin and dense halide solid electrolyte layer through magnetron sputtering, thereby effectively improving the rate performance and cycle performance of the solid-state lithium-ion battery.

[0004] One aspect of the present invention provides an all-solid-state thin-film lithium battery, comprising a halide solid electrolyte layer, wherein the halide solid electrolyte layer is prepared by magnetron sputtering.

[0005] In some embodiments, the ionic conductivity λ of the halide solid electrolyte layer satisfies: λ≥10 -4 S / cm.

[0006] In some embodiments, the thickness of the halide solid electrolyte layer is 0.5 μm to 1.5 μm.

[0007] In some embodiments, the halide solid electrolyte layer includes Li a M b X 6 , wherein M includes one or more of Zr, Hf, In, Sc, Y, La, Ce, Pr, Nb, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; X includes one or more of F, Cl, Br, and I; a>0, and a+b=6.

[0008] Another aspect of the present invention provides a method for preparing an all-solid-state thin-film lithium battery, comprising the following steps:

[0009] 1) preparing a first electrode;

[0010] 2) forming a halide solid electrolyte layer on the first electrode by a magnetron sputtering method;

[0011] 3) forming a second electrode on a surface of the halide solid electrolyte layer away from the first electrode, wherein the first electrode has opposite polarity to the second electrode;

[0012] The first electrode and the second electrode are arranged on opposite sides of the halide solid electrolyte layer without contacting each other.

[0013] The first electrode is a positive electrode or a negative electrode, and the second electrode is a negative electrode or a positive electrode.

[0014] In some embodiments, in step 2), the magnetron sputtering step includes using Li a+x M b X 6 The target material is sputtered, wherein M includes one or more of Zr, Hf, In, Sc, Y, La, Ce, Pr, Nb, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; X includes one or more of F, Cl, Br, and I; a>0, a+b=6, and x>0.

[0015] In some embodiments, step 1) includes forming a first electrode on the substrate by magnetron sputtering.

[0016] In some embodiments, step 3) includes forming the second electrode on a surface of the halide solid electrolyte layer away from the first electrode by magnetron sputtering.

[0017] In some embodiments, step 3) includes forming a current collector layer on the surface of the second electrode.

[0018] In some embodiments, the magnetron sputtering process includes:

[0019] After cleaning the surface of the substrate, place it in the vacuum chamber of the magnetron sputtering machine;

[0020] Argon gas was introduced into the vacuum chamber to perform magnetron sputtering.

[0021] In some preferred embodiments, in the magnetron sputtering step, the argon gas flow rate is 30 sccm to 50 sccm.

[0022] In some preferred embodiments, in the magnetron sputtering step, the gas pressure during sputtering is 0.5Pa to 0.8Pa.

[0023] In some preferred embodiments, in the magnetron sputtering step, the radio frequency power is 50W to 200W.

[0024] In some preferred embodiments, in the magnetron sputtering step, the sputtering temperature is room temperature.

[0025] In some embodiments, when the negative electrode is lithium metal or lithium alloy, a second electrolyte layer is further included between the solid electrolyte layer and the negative electrode layer. The second electrolyte is a solid electrolyte that is stable to lithium.

[0026] Compared with the prior art, the beneficial technical effect of the present application is: the all-solid-state thin-film lithium battery prepared in the present application can effectively improve the rate performance of the all-solid-state thin-film lithium battery by using a halide solid electrolyte layer as a transmission medium for lithium ions between the positive electrode and the negative electrode.

[0027] Moreover, the use of magnetron sputtering to prepare the halide solid electrolyte layer is beneficial to improving the amorphization degree of the halide solid electrolyte, improving the ion transport capacity of the halide solid electrolyte layer, and improving the rate performance of the all-solid-state thin-film lithium battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a SEM image of the solid electrolyte layer prepared in Example 1. DETAILED DESCRIPTION

[0029] References to embodiments of the present application will now be provided in detail, one or more examples of which are described below. Each example is provided as an explanation rather than a limitation of the present application. In fact, it will be apparent to those skilled in the art that various modifications and variations may be made to the present application without departing from the scope or spirit of the present application. For example, a feature described or described as part of one embodiment may be used in another embodiment to produce a further embodiment.

[0030] Therefore, it is intended that the present application covers such modifications and variations that fall within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present application are disclosed in or are apparent from the following detailed description. It will be appreciated by those of ordinary skill in the art that this discussion is merely a description of exemplary embodiments and is not intended to limit the broader aspects of the present application.

[0031] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0032] In this application, when it comes to numerical ranges, unless otherwise specified, the above numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0033] If there is no special description, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution. If there is no special description, all technical features and optional technical features of the present application can be combined with each other to form a new technical solution.

[0034] If there is no special explanation, all steps of the present application can be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, it is mentioned that the method may also include step (c), which means that step (c) can be added to the method in any order. For example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0035] If there is no special explanation, the "include" and "comprising" mentioned in this application represent open-ended or closed-ended expressions. For example, "include" and "comprising" may represent that other components not listed may also be included or only listed components may be included or only listed components may be included.

[0036] Most of the existing all-solid-state thin-film lithium batteries use LIPON as the lithium ion transmission medium, and the lithium ion transmission capacity cannot meet higher requirements.

[0037] In order to further improve the rate performance of all-solid-state thin-film lithium batteries, this application adopts the following technical solutions:

[0038] In a first aspect, the present application provides an all-solid-state thin-film lithium battery, comprising a halide solid electrolyte layer, wherein the halide solid electrolyte layer is prepared by magnetron sputtering.

[0039] The improvement of the amorphization degree of the halide solid electrolyte is beneficial to the improvement of its ionic conductivity, and the use of magnetron sputtering to prepare the halide solid electrolyte layer is beneficial to improving the amorphization degree of the halide solid electrolyte, improving the ion transmission capacity of the halide solid electrolyte layer, and improving the rate performance of the all-solid-state thin-film lithium battery.

[0040] In some embodiments, the ionic conductivity λ of the halide solid electrolyte layer satisfies: λ≥10 -4 S / cm.

[0041] Compared with LIPON, halide solid electrolytes have higher ionic conductivity, which is beneficial to improving the rate performance of all-solid-state thin-film lithium batteries.

[0042] In some embodiments, the thickness of the halide solid electrolyte layer is 0.5 μm to 1.5 μm.

[0043] In some embodiments, the halide solid electrolyte layer includes Li a M b X 6 , wherein M includes one or more of Zr, Hf, In, Sc, Y, La, Ce, Pr, Nb, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; X includes one or more of F, Cl, Br, and I; a>0, and a+b=6.

[0044] It is understandable that, in other embodiments, the halide solid electrolyte may also be other halide solid electrolytes capable of magnetron sputtering, such as Li a M b X 6 Halide solid electrolytes doped with metal and halogen sites, such as Li 2.8 In 0.5 Zr 0.5 Cl 5 O 0.55 wait;

[0045] In some embodiments, when the negative electrode is lithium metal or lithium alloy, a second electrolyte layer is further included between the solid electrolyte layer and the negative electrode layer, and the second electrolyte is a solid electrolyte that is stable to lithium.

[0046] In some embodiments, the second electrolyte includes LiPON, Li 2 O, LiF, Li 3 N.Li 2 One of S.

[0047] Another aspect of the present invention provides a method for preparing an all-solid-state thin-film lithium battery, comprising the following steps:

[0048] 1) preparing a first electrode;

[0049] 2) forming a halide solid electrolyte layer on the first electrode by a magnetron sputtering method;

[0050] 3) forming a second electrode on a surface of the halide solid electrolyte layer away from the first electrode, wherein the first electrode has opposite polarity to the second electrode;

[0051] The first electrode and the second electrode are arranged on opposite sides of the halide solid electrolyte layer without contacting each other.

[0052] The use of magnetron sputtering to prepare the halide solid electrolyte layer is beneficial to improving the amorphization degree of the halide solid electrolyte and the ion transport capacity of the halide solid electrolyte layer. Moreover, no annealing is required after magnetron sputtering, which is beneficial to simplifying the process and reducing costs.

[0053] In some embodiments, in step 2), the magnetron sputtering step includes using Li a+x M b X 6 The target material is sputtered, wherein M includes one or more of Zr, Hf, In, Sc, Y, La, Ce, Pr, Nb, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; X includes one or more of F, Cl, Br, and I; a>0, a+b=6, and x>0. It can be understood that by increasing the content of Li in the target material, the consumption of Li during the sputtering process is prevented.

[0054] In some embodiments, step 1) includes forming a first electrode on a substrate by magnetron sputtering, the substrate includes a conductive substrate and a non-conductive substrate coated with a current collector, and the current collector coating on the non-conductive substrate includes Au, Pt, Ti, Ni, etc.

[0055] In some preferred embodiments, in step 1), the substrate comprises a rigid substrate, and the thickness of the current collector coating on the surface of the rigid substrate satisfies: 10-50 nm.

[0056] As one implementation manner, the rigid substrate includes silicon wafer, quartz glass, corundum, etc.

[0057] In some preferred embodiments, the substrate in step 1) includes a flexible substrate. When the substrate is a non-conductive flexible substrate, before step 1) the process further includes forming a current collector layer on the flexible substrate by sputtering.

[0058] As one implementation mode, the conductive flexible substrate includes gold, nickel, platinum, copper, cobalt, titanium, stainless steel foil, etc.; the non-conductive flexible substrate includes polyimide, mica, etc.

[0059] In some embodiments, step 3) includes forming the second electrode on a surface of the halide solid electrolyte layer away from the first electrode by magnetron sputtering.

[0060] In some embodiments, step 3) includes forming a current collector layer on the surface of the second electrode.

[0061] In some embodiments, the magnetron sputtering process includes:

[0062] After cleaning the surface of the substrate, place it in the vacuum chamber of the magnetron sputtering machine;

[0063] Argon gas was introduced into the vacuum chamber to perform magnetron sputtering.

[0064] In some preferred embodiments, in the magnetron sputtering step, the argon gas flow rate is 30 sccm to 50 sccm.

[0065] In some preferred embodiments, in the magnetron sputtering step, the gas pressure during sputtering is 0.5Pa to 0.8Pa.

[0066] In some preferred embodiments, in the magnetron sputtering step, the RF power is 50W~200W.

[0067] In some preferred embodiments, in the magnetron sputtering step, the sputtering temperature is room temperature.

[0068] In some embodiments, the first electrode is a positive electrode and the second electrode is a negative electrode.

[0069] In some embodiments, the first electrode is a cathode and the second electrode is a cathode.

[0070] In some embodiments, the positive electrode includes a positive electrode active material, which is a compound capable of reversibly intercalating and deintercalating lithium.

[0071] In some embodiments, the positive electrode active material comprises one or more transition metal cations, such as manganese (Mn), nickel (Ni), cobalt (Co), chromium (Cr), iron (Fe), vanadium (V), and combinations thereof.

[0072] In some embodiments, the positive electrode active material is one of a layered oxide, a spinel, and a polyanion. For example, the layered oxide (e.g., a rock salt layered oxide) comprises one or more lithium-based positive electrode active materials selected from the following: LiCoO 2 (LCO), LiNi x Mn y Co 1-x-y O 2 (where 0≤x≤1 and 0≤y≤1), LiNi 1-x-y Co x Al y O 2 (where 0≤x≤1 and 0≤y≤1), LiNi x Mn 1-x O 2 (where 0≤x≤1), and LiMO 2 (wherein M is one of Mn, Ni, Co and Al and 0≤x≤1). The spinel comprises one or more lithium-based positive active materials selected from the group consisting of: LiMn 2 O 4 (LMO) and LiNixMn 1.5 O 4 The olivine type contains one or more lithium-based positive electrode active materials LiMPO 4(wherein M is at least one of Fe, Ni, Co and Mn). The polyanion cation includes, for example, phosphates such as LiV 2 (PO 4 ) 3 and / or silicates such as LiFeSiO 4 .

[0073] In some embodiments, the negative electrode includes a negative electrode active material. In some embodiments, a carbon material can be selected as the negative electrode active material, and specifically one or more of the following can be selected: graphite, needle coke, amorphous carbon, a carbon-containing mesophase, carbon fiber, and a carbon material with a low degree of graphitization. Among them, graphite can include natural graphite, artificial graphite, etc. In addition, materials obtained by coating them with carbon materials, such as amorphous carbon and graphitized materials can also be used. Amorphous carbon includes, but is not limited to, particles obtained by firing the entire mesophase, and particles obtained by infusible treatment and firing of a carbon precursor. As carbonaceous particles with a low degree of graphitization, particles obtained by firing organic matter at a temperature generally below 2500°C can be listed.

[0074] In addition, non-metallic materials that can be used as negative electrode active materials also include silicon and its compounds, such as Si, SiOx (0≤x<2). Since silicon-containing materials are prone to expansion, easy to fall off from the negative electrode current collector, and have poor conductivity, they are often mixed with carbon materials, such as core-shell structures containing carbon coating layers.

[0075] It is understood that the above examples of positive and negative electrodes are merely illustrative, and any known positive electrode active material and negative electrode active material can be used in the present application without violating the inventive concept of the present application. And the addition of known additives based on actual use requirements should also be considered within the scope of protection of the present application.

[0076] The following are specific embodiments.

[0077] Example 1

[0078] Preparation of all-solid-state thin-film lithium batteries:

[0079] 1) Preparation of positive electrode: prepare a stainless steel substrate, fix it on the base plate of the radio frequency magnetron sputtering equipment, and form a positive electrode on the stainless steel substrate by sputtering. The positive electrode is lithium cobalt oxide;

[0080] 2) forming a halide solid electrolyte layer on the positive electrode by magnetron sputtering;

[0081] Target material selection: Li 2.25 ZrCl 6 The magnetron sputtering chamber is evacuated until the vacuum degree is less than 1×10 −5Pa. The working gas is Ar, the Ar gas flow rate is 40 sccm; the gas pressure is 0.5 Pa; the distance between the target and the cathode layer is kept at 10 cm, the sputtering power is set to 100 W, and the sputtering temperature is room temperature.

[0082] The thickness of the halide solid electrolyte layer is 0.73 μm.

[0083] 3) A negative electrode is formed on the surface of the halide solid electrolyte layer away from the positive electrode, and the positive electrode and the negative electrode are opposite to each other and not in contact with each other through the solid electrolyte layer; the negative electrode is Si.

[0084] 4) Sputtering forms a copper current collector layer on the negative electrode to form an all-solid-state thin-film lithium battery.

[0085] Example 2

[0086] Preparation of all-solid-state thin-film lithium batteries:

[0087] 1) Preparation of positive electrode: prepare a stainless steel substrate, fix it on the base plate of the radio frequency magnetron sputtering equipment, and form a positive electrode on the stainless steel substrate by sputtering. The positive electrode is lithium cobalt oxide;

[0088] 2) forming a halide solid electrolyte layer on the positive electrode by magnetron sputtering;

[0089] Target material selection: Li 2.25 ZrCl 6 The magnetron sputtering chamber is evacuated until the vacuum degree is less than 1×10 −5 Pa. The working gas is Ar, the Ar gas flow rate is 30 sccm; the gas pressure is 0.5 Pa; the distance between the target and the cathode layer is kept at 10 cm, the sputtering power is set to 50 W, and the sputtering temperature is room temperature.

[0090] The thickness of the halide solid electrolyte layer was 0.51 μm.

[0091] 5) A negative electrode is formed on the surface of the halide solid electrolyte layer away from the positive electrode, and the positive electrode and the negative electrode are opposite to each other and not in contact with each other through the solid electrolyte layer; the negative electrode is Si.

[0092] 6) Sputtering forms a copper current collector layer on the negative electrode to form an all-solid-state thin-film lithium battery.

[0093] Example 3

[0094] Preparation of all-solid-state thin-film lithium batteries:

[0095] 1) Preparation of positive electrode: prepare a stainless steel substrate, fix it on the base plate of the radio frequency magnetron sputtering equipment, and form a positive electrode on the stainless steel substrate by sputtering. The positive electrode is lithium cobalt oxide;

[0096] 2) forming a halide solid electrolyte layer on the positive electrode by magnetron sputtering;

[0097] Target material selection: Li 2.25 ZrCl 6 The magnetron sputtering chamber is evacuated until the vacuum degree is less than 1×10 −5 Pa. The working gas is Ar, the Ar gas flow rate is 50 sccm; the gas pressure is 0.8 Pa; the distance between the target and the cathode layer is kept at 10 cm, the sputtering power is set to 200 W, and the sputtering temperature is room temperature.

[0098] The thickness of the halide solid electrolyte layer is 1.52 μm.

[0099] 3) A negative electrode is formed on the surface of the halide solid electrolyte layer away from the positive electrode, and the positive electrode and the negative electrode are opposite to each other and not in contact with each other through the solid electrolyte layer; the negative electrode is Si.

[0100] 4) Sputtering forms a copper current collector layer on the negative electrode to form an all-solid-state thin-film lithium battery.

[0101] Example 4

[0102] Preparation of all-solid-state thin-film lithium batteries:

[0103] 1) Preparation of positive electrode: prepare a stainless steel substrate, fix it on the base plate of the radio frequency magnetron sputtering equipment, and form a positive electrode on the stainless steel substrate by sputtering. The positive electrode is lithium cobalt oxide;

[0104] 2) forming a halide solid electrolyte layer on the positive electrode by magnetron sputtering;

[0105] Target material selection: Li 3.375 ScCl 6 The magnetron sputtering chamber is evacuated until the vacuum degree is less than 1×10 −5 Pa. The working gas is Ar, the Ar gas flow rate is 50 sccm; the gas pressure is 0.8 Pa; the distance between the target and the cathode layer is kept at 10 cm, the sputtering power is set to 150 W, and the sputtering temperature is room temperature.

[0106] The thickness of the halide solid electrolyte layer is 1.24 μm.

[0107] 3) A negative electrode is formed on the surface of the halide solid electrolyte layer away from the positive electrode, and the positive electrode and the negative electrode are opposite to each other and not in contact with each other through the solid electrolyte layer; the negative electrode is Si.

[0108] 4) Sputtering forms a copper current collector layer on the negative electrode to form an all-solid-state thin-film lithium battery.

[0109] Example 5

[0110] Preparation of all-solid-state thin-film lithium batteries:

[0111] 1) Preparation of positive electrode: prepare a stainless steel substrate, fix it on the base plate of the radio frequency magnetron sputtering equipment, and form a positive electrode on the stainless steel substrate by sputtering. The positive electrode is lithium cobalt oxide;

[0112] 2) forming a solid electrolyte layer on the positive electrode by magnetron sputtering;

[0113] Target material selection: Li 2.8 In 0.5 Zr 0.5 Cl 5 O 0.5 The magnetron sputtering chamber is evacuated until the vacuum degree is less than 1×10 −5 Pa. The working gas is Ar, the Ar gas flow rate is 40 sccm; the gas pressure is 0.8 Pa; the distance between the target and the cathode layer is kept at 10 cm, the sputtering power is set to 120 W, and the sputtering temperature is room temperature.

[0114] The thickness of the halide solid electrolyte layer is 0.96 μm.

[0115] 3) A negative electrode is formed on the surface of the halide solid electrolyte layer away from the positive electrode, and the positive electrode and the negative electrode are opposite to each other and not in contact with each other through the solid electrolyte layer; the negative electrode is Si.

[0116] 4) Sputtering forms a copper current collector layer on the negative electrode to form an all-solid-state thin-film lithium battery.

[0117] Example 6

[0118] Preparation of all-solid-state thin-film lithium batteries:

[0119] 1) Preparation of positive electrode: prepare a flexible substrate mica, fix it on the substrate of the radio frequency magnetron sputtering equipment, form a current collector layer on the flexible substrate by sputtering, and then form a positive electrode by sputtering. The positive electrode is lithium cobalt oxide;

[0120] 2) forming a halide solid electrolyte layer on the positive electrode by magnetron sputtering;

[0121] Target material selection: Li 2.25 ZrCl 6 The magnetron sputtering chamber is evacuated until the vacuum degree is less than 1×10 −5 Pa. The working gas is Ar, the Ar gas flow rate is 50 sccm; the gas pressure is 0.5 Pa; the distance between the target and the cathode layer is kept at 10 cm, the sputtering power is set to 120 W, and the sputtering temperature is room temperature.

[0122] The thickness of the halide solid electrolyte layer is 0.82 μm.

[0123] 3) A negative electrode is formed on the surface of the halide solid electrolyte layer away from the positive electrode, and the positive electrode and the negative electrode are opposite to each other and not in contact with each other through the solid electrolyte layer; the negative electrode is Si.

[0124] 4) Sputtering forms a copper current collector layer on the negative electrode to form an all-solid-state thin-film lithium battery.

[0125] Comparative Example 1

[0126] The difference between Comparative Example 1 and Example 1 is that the all-solid-state thin-film lithium battery includes a positive electrode, a negative electrode and a LIPON solid electrolyte layer.

[0127] Test Case

[0128] 1. Thickness test:

[0129] According to GB / T 6672-2001 standard, the thickness of the solid electrolyte layer in Examples 1 to 5 and Comparative Example 1 was measured using a Millimar C1208 film thickness gauge (Millimar, Germany).

[0130] And, the thickness of the solid electrolyte layer=the total thickness after sputtering-the thickness of the first electrode.

[0131] 2. Cycle performance test

[0132] The assembled battery was charged and discharged in the voltage range of 3~4.5V, with a rate of 0.05C for the first two cycles and a rate of 0.1C from the third cycle onwards. The cycle was cycled to the 200th cycle and the cycle retention rate was recorded. The cycle retention rate = discharge capacity at the 200th cycle / discharge capacity at the 3rd cycle.

[0133] 3. Rate performance:

[0134] At a temperature of 25°C, the fully charged battery is discharged at a current of 0.1C to a cut-off voltage of 3.0V, and the capacity obtained by the test is C0;

[0135] At a temperature of 25°C, a fully charged battery is discharged at a current of 3C to a cut-off voltage of 3.0V. The capacity obtained by the test is C1, and C1 / C0 is the rate retention rate in the table below.

[0136] The solid electrolytes and all-solid-state batteries prepared in Examples 1 to 6 and Comparative Example 1 were tested, and the test results are shown in Table 1 below.

[0137] Table 1

[0138]

[0139] As can be seen from Table 1 above, by using a halide solid electrolyte layer as the solid electrolyte membrane of an all-solid-state thin-film lithium battery, the rate performance of the all-solid-state thin-film lithium battery can be effectively improved. At the same time, the all-solid-state thin-film lithium battery also has good cycle performance.

[0140] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0141] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. All-solid-state thin-film lithium battery, characterized in that: The invention comprises a solid electrolyte layer, wherein the halide solid electrolyte layer is prepared by magnetron sputtering.

2. The all-solid-state thin-film lithium battery according to claim 1, characterized in that: The ionic conductivity λ of the halide solid electrolyte layer satisfies: λ≥10 -4 S / cm.

3. The all-solid-state thin-film lithium battery according to claim 1, characterized in that: The halide solid electrolyte layer includes Li a M b X6, wherein M includes one or more of Zr, Hf, In, Sc, Y, La, Ce, Pr, Nb, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; X includes one or more of F, Cl, Br, and I; a>0, and a+b=6.

4. The all-solid-state thin-film lithium battery according to claim 1, characterized in that: The thickness of the halide solid electrolyte layer is 0.5 μm to 1.5 μm.

5. The method for preparing an all-solid-state thin-film lithium battery according to claim 1, characterized in that: The steps include: 1) preparing a first electrode; 2) forming a halide solid electrolyte layer on the first electrode by magnetron sputtering; 3) forming a second electrode on a surface of the halide solid electrolyte layer away from the first electrode; The first electrode has opposite polarity to the second electrode.

6. The preparation method according to claim 5, characterized in that: In step 2), the magnetron sputtering step includes using Li a+x M b X6 target material is sputtered, wherein M includes one or more of Zr, Hf, In, Sc, Y, La, Ce, Pr, Nb, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; X includes one or more of F, Cl, Br, and I; a>0, a+b=6, and x>0.

7. The preparation method according to claim 5, characterized in that: Step 1) includes forming the first electrode on the substrate by magnetron sputtering.

8. The preparation method according to claim 5, characterized in that: The step 3) includes forming a second electrode on a surface of the halide solid electrolyte layer away from the first electrode by magnetron sputtering.

9. The preparation method according to claim 5, characterized in that: In the step 2), the magnetron sputtering process includes: After cleaning the surface of the substrate, place it in the vacuum chamber of the magnetron sputtering machine; Argon gas is introduced into the vacuum chamber to perform magnetron sputtering; Preferably, in the magnetron sputtering step, the argon gas flow rate is 30 sccm to 50 sccm; Preferably, in the magnetron sputtering step, the gas pressure during sputtering is 0.5Pa to 0.8Pa. Preferably, in the magnetron sputtering step, the radio frequency power is 50W to 200W.

10. The preparation method according to claim 5, characterized in that: In the step 2), in the magnetron sputtering step, the sputtering temperature is room temperature.

Images