Solid-state battery, solid-state electrolyte material, and electric device

Abstract

A solid-state battery, a solid-state electrolyte material, and an electric device. The solid-state battery comprises a positive electrode sheet, a first solid-state electrolyte membrane, a second solid-state electrolyte membrane, and a negative electrode sheet which are sequentially stacked. The negative electrode sheet is a lithium metal negative electrode; the material of the first solid-state electrolyte membrane comprises a sulfide solid-state electrolyte; and the material of the second solid-state electrolyte membrane comprises a compound having a general formula of Li7-2x-na+yGaxLabM1yZr2-aQaO12, wherein 0<x≤0.3, 0≤y≤0.5, 0≤a≤0.8, 0<b≤3, M1 comprises one or more of main-group II metal elements, Q comprises one or more of main-group I metal elements, subgroup III metal elements, main-group V metal elements, subgroup V metal elements, main-group VI metal elements, and subgroup VI metal elements, the valence of Q is V1, n=V1-4, -2≤n≤1, and 5.2≤7-2x-na+y≤7.1. The solid-state battery can have relatively high battery capacity, cycle performance and rate performance.

Description

Solid-state batteries, solid-state electrolyte materials and electrical devices

[0001] Related applications

[0002] This application claims priority to Chinese patent application No. 2024119965166, filed on December 31, 2024, entitled "Solid-state battery, solid-state electrolyte material and electrical device", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This application relates to the field of secondary battery technology, and more particularly to a solid-state battery, a solid electrolyte material, and an electrical device. Background Technology

[0004] Solid-state batteries use a non-flammable solid electrolyte instead of the organic electrolyte in traditional liquid secondary batteries, significantly improving battery safety and are considered the next generation of batteries closest to industrialization. At the same time, solid-state batteries have also attracted considerable attention due to their superior energy density.

[0005] Solid electrolytes are the core of all-solid-state batteries, and their performance significantly impacts the entire battery. Among all current solid electrolyte systems, sulfide-based solid electrolytes have received extensive research due to their high room-temperature conductivity (1 mS / cm to 10 mS / cm) and excellent mechanical properties. Furthermore, compared to traditional graphite anodes, using lithium metal as the anode can theoretically increase battery capacity by approximately 10 times. However, because sulfide-based solid electrolytes have a narrow electrochemical stability window and react violently with lithium metal, their cycle performance and rate performance deteriorate significantly. Therefore, sulfide-based solid electrolytes are unsuitable as the electrolyte layer in lithium metal solid-state batteries. This is why it is currently difficult to simultaneously achieve optimal battery capacity, cycle performance, and rate performance in solid-state batteries. Summary of the Invention

[0006] To achieve the above objectives, this application provides a solid-state battery, solid-state electrolyte material, and electrical device that can balance high battery capacity with cycle performance and rate performance.

[0007] A first aspect of this application provides a solid-state battery, comprising a positive electrode, a first solid electrolyte membrane, a second solid electrolyte membrane, and a negative electrode stacked sequentially; the negative electrode is a lithium metal negative electrode; the material of the first solid electrolyte membrane includes a sulfide solid electrolyte.

[0008] The material of the second solid electrolyte membrane includes Li 7-2x-na+y Ga x La b M1 y Zr 2-a Qa O 12 The compounds are defined as follows: 0 < x ≤ 0.3, 0 ≤ y ≤ 0.5, 0 ≤ a ≤ 0.8, 0 < b ≤ 3. M1 includes one or more of the main group II metal elements, and Q includes one or more of the main group I metal elements, the subgroup III metal elements, the main group V and subgroup V metal elements, and the main group VI and subgroup V metal elements. The valence of Q is V1, n = V1 - 4, -2 ≤ n ≤ 1, 5.2 ≤ 7 - 2x - na + y ≤ 7.1.

[0009] The aforementioned solid-state battery uses a lithium metal anode to increase the battery's capacity. At the same time, a compound with the above-mentioned general formula is placed between the lithium metal anode and the electrolyte membrane of the sulfide solid electrolyte as a second solid electrolyte membrane, which enables the battery to have high capacity while exhibiting good cycle performance and rate performance.

[0010] In some embodiments, M1 includes one or more of Ba, Mg, Ca and Sr elements; optionally, M1 includes one or more of Ba, Mg and Ca elements.

[0011] In some implementations, Q includes one or more of the elements Ta, Nb, W, Sb, Gd, Y, and Rb; optionally, Q includes the element Ta.

[0012] In some implementations, the general formula is Li 7-2x-na+y Ga x La b M1 y Zr 2-a Q a O 12 The compounds include Li 6.5 Ga 0.1 La 2.8 Ba 0.2 Zr 1.6 Ta 0.4 O 12 Li 6.5 Ga 0.1 La 2.8 Mg 0.2 Zr 1.6 Ta 0.4 O 12 Li 6.5 Ga 0.1 La 2.8 Ca 0.2 Zr 1.6 Ta 0.4 O 12 Li 6.5 Ga 0.2 La2.5 Ba 0.5 Zr 1.6 Dad 0.4 O 12 、Li 6.5 Ga 0.1 Day 2.8 Mg 0.2 Zr 1.6 No 0.4 O 12 、Li 5.9 Ga 0.3 Day 2.8 Mg 0.2 Zr 1.6 No 0.4 O 12 、Li 5.9 Ga 0.3 Day 2.8 Mg 0.2 Zr 1.6 Dad 0.4 O 12 、Li 6.6 Ga 0.2 La3Zr 1.6 Dad 0.4 O 12 、Li 6.5 Ga 0.3 Day 2.8 Ba 0.2 Zr2O 12 、Li 5.2 Ga 0.8 Day 2.8 Approx 0.2 Zr 1.6 Dad 0.4 O 12 、Li 6.5 Ga 0.1 Day 2.8 Ba 0.2 Zr 1.8 Sb 0.2 O 12 、Li 6.5 Ga 0.1 Day 2.8 Ba 0.2 Zr 1.6 W 0.4 O 12 、Li 6.95 Ga 0.2 Day 2.8 Ba 0.2 Zr 1.95 Dad 0.05 O 12 、Li7Ga 0.2 Day 2.8 Ba0.2 Zr 1.9 Y 0.1 O 12 and Li 7.1 Ga 0.2 La 2.8 Ba 0.2 Zr 1.9 Rb 0.1 O 12、 One or more of them.

[0013] In some implementations, the general formula is Li 7-2x-na+y Ga x La b M1 y Zr 2-a Q a O 12 The compound is a garnet-type compound. Using a garnet-type compound can further improve the ionic conductivity of the compound, while also having good compatibility with lithium metal anodes, thus comprehensively improving cycle performance and rate performance.

[0014] In some embodiments, a metal layer is further disposed on the side of the second solid electrolyte membrane near the negative electrode. The introduction of the metal layer enables the formation of a metal-Li alloy when combined with the lithium metal negative electrode, reducing the interfacial impedance between the second solid electrolyte membrane and the lithium metal negative electrode, and improving cycle performance and rate performance.

[0015] Furthermore, the metal layer includes one or more of the elements Au, Ag, and Zn.

[0016] Furthermore, the thickness of the metal layer is 14nm to 34nm.

[0017] In some embodiments, the solid-state battery further includes a third solid-state electrolyte membrane disposed between the positive electrode and the first solid-state electrolyte membrane; the third solid-state electrolyte membrane has one or both of the following characteristics:

[0018] (1) The materials of the third solid electrolyte membrane and the second solid electrolyte membrane each independently include those with the general formula Li. 7-2x-na+y Ga x La b M1 y Zr 2-a Q a O 12 Compounds;

[0019] (2) The thickness of the third solid electrolyte membrane is 0.1 mm to 0.7 mm.

[0020] By also placing the above-mentioned general formula compound between the positive electrode and the sulfide solid electrolyte, the side reactions between the positive electrode material and the sulfide solid electrolyte can be reduced, thereby improving the cycle performance and rate performance of the battery.

[0021] In some embodiments, the thickness of the first solid electrolyte membrane is 0.9 mm to 1.4 mm.

[0022] In some embodiments, the thickness of the second solid electrolyte membrane is 0.1 mm to 0.7 mm.

[0023] In some embodiments, the positive electrode includes a positive active layer, the material of which includes a positive active material and a halide solid electrolyte. By introducing a halide solid electrolyte into the positive active layer, the contact between the positive active material and the sulfide solid electrolyte can be further reduced, thereby reducing the occurrence of side reactions.

[0024] In some embodiments, the halide solid electrolyte includes Li3M2Cl6, where M2 includes one or more group III main and subgroup metal elements;

[0025] Optionally, M2 includes one or more of the following elements: In, Y, La, Sc, Er, Yb, and Ho.

[0026] A second aspect of this application provides a solid electrolyte material, comprising the general formula Li 7-2x-na+y Ga x La b M1 y Zr 2-a Q a O 12 The compounds are defined as follows: 0 < x ≤ 0.3, 0 ≤ y ≤ 0.5, 0 ≤ a ≤ 0.8, 0 < b ≤ 3. M1 includes one or more of the main group II metal elements, and Q includes one or more of the main group I metal elements, the subgroup III metal elements, the main group V and subgroup V metal elements, and the main group VI and subgroup V metal elements. The valence of Q is V1, n = V1 - 4, -2 ≤ n ≤ 1, 5.2 ≤ 7 - 2x - na + y ≤ 7.1.

[0027] In some embodiments, the solid electrolyte material is the material of the second solid electrolyte membrane in a solid-state battery as described above.

[0028] A third aspect of this application provides an electrical device comprising a solid-state battery as described above or a solid-state electrolyte material as described above. Attached Figure Description

[0029] To better describe and illustrate the embodiments or examples provided in this application, reference may be made to one or more accompanying drawings. Additional details or examples used to describe the drawings should not be considered as limiting the scope of any of the disclosed applications, the currently described embodiments or examples, or the best mode of conduct of these applications as currently understood. Furthermore, the same reference numerals denote the same parts throughout the drawings. In the drawings:

[0030] Figure 1 is a schematic diagram of a solid-state battery cell according to an embodiment of this application.

[0031] Figure 2 is an exploded view of a solid-state battery cell according to an embodiment of this application shown in Figure 1.

[0032] Figure 3 is a schematic diagram of a battery device according to an embodiment of this application.

[0033] Figure 4 is a schematic diagram of a battery pack according to one embodiment of this application.

[0034] Figure 5 is an exploded view of the battery pack of one embodiment of this application shown in Figure 4.

[0035] Figure 6 is a schematic diagram of an electrical device using a solid-state battery as a power source according to an embodiment of this application.

[0036] Figure 7 is a SEM scan of the oxide electrolyte prepared in Example 1 of this application.

[0037] Explanation of reference numerals in the attached drawings: 1, battery pack; 2, upper casing; 3, lower casing; 4, battery assembly; 5, solid-state battery cell; 51, casing; 52, solid-state battery cell; 53, cover plate; 6, electrical device. Detailed Implementation

[0038] To facilitate understanding of this application, a more complete description will be provided below with reference to the accompanying drawings. Preferred embodiments of this application are shown in the drawings. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of this application.

[0039] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0040] The "range" disclosed in this application can be defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of the specific range. Ranges defined in this way can include or exclude endpoints. Any endpoint can be included or excluded independently, and they can be combined arbitrarily; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60–120 and 80–110 are listed for a specific parameter, it is expected that ranges of 60–110 and 80–120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are also listed, then the following ranges are all expected: 1–3, 1–4, 1–5, 2–3, 2–4, and 2–5. In this application, unless otherwise stated, the numerical range "a–b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0" and "5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is described as an integer ≥ 2, it is equivalent to listing integers such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For instance, when a parameter is described as an integer selected from "2-10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0041] In this application, the terms "multiple" or "various" are used unless otherwise specified, referring to a quantity greater than or equal to 2. For example, "one or more" means one or more types.

[0042] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0043] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment or implementation of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments. The term "implementation" as used herein has a similar understanding.

[0044] Those skilled in the art will understand that the order in which the steps are written in the methods of various embodiments or examples does not imply a strict execution order and does not constitute any limitation on the implementation process. The detailed execution order of each step should be determined by its function and possible internal logic. Unless otherwise specified, all steps of this application may be performed sequentially or randomly, preferably sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, if the method may also include step (c), it 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 it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0045] In this application, unless otherwise specified, A (e.g., B) means that B is a non-limiting example of A, and it is understood that A is not limited to B.

[0046] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0047] In traditional solid-state batteries, it is difficult to combine sulfide solid electrolytes with lithium metal anodes, resulting in a trade-off between battery capacity, cycle performance, and rate performance. Compared to sulfide electrolytes, oxide electrolytes exhibit good stability at higher oxidation potentials and possess a wider electrochemical stability window (>6V vs. Li). + While oxide electrolytes (Li) are stable for lithium metal, traditional oxide electrolytes have lower ionic conductivity than sulfide electrolytes and poorer interfacial contact with the lithium metal anode, thus failing to effectively address the aforementioned problems.

[0048] One embodiment of this application provides a solid-state battery, comprising a positive electrode, a first solid electrolyte membrane, a second solid electrolyte membrane, and a negative electrode stacked sequentially; the negative electrode is a lithium metal negative electrode; the material of the first solid electrolyte membrane includes a sulfide solid electrolyte.

[0049] The material of the second solid electrolyte membrane includes Li 7-2x-na+y Ga x La b M1 y Zr 2-a Q a O 12The compounds are defined as follows: 0 < x ≤ 0.3, 0 ≤ y ≤ 0.5, 0 ≤ a ≤ 0.8, 0 < b ≤ 3. M1 includes one or more of the main group II metal elements, and Q includes one or more of the main group I metal elements, the subgroup III metal elements, the main group V and subgroup V metal elements, and the main group VI and subgroup V metal elements. The valence of Q is V1, n = V1 - 4, -2 ≤ n ≤ 1, 5.2 ≤ 7 - 2x - na + y ≤ 7.1.

[0050] The aforementioned solid-state battery uses a lithium metal anode to increase battery capacity. Simultaneously, a compound with the aforementioned general formula is placed between the lithium metal anode and the electrolyte membrane of the sulfide solid electrolyte as a second solid electrolyte membrane. On one hand, this reduces direct contact between the lithium metal anode and the sulfide solid electrolyte, thereby reducing side reactions between them. On the other hand, the introduction of Ga element in this compound gives it high ionic conductivity, reduces interfacial impedance, and the compound has good stability, making it less prone to short circuits due to lithium dendrite formation during cycling. Thus, the battery achieves high capacity while exhibiting good cycle performance and rate performance.

[0051] Without limitation, the chemical formula of the material of the first electrolyte layer can be obtained by methods such as X-ray diffraction (XRD) or energy-dispersive X-ray spectroscopy (EDS).

[0052] Specifically, the value of x includes, but is not limited to: 0.01, 0.05, 0.08, 0.1, 0.12, 0.15, 0.17, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, or any two of the above.

[0053] Specifically, the values ​​of y include, but are not limited to: 0, 0.1, 0.2, 0.3, 0.4, 0.5, or any two of the aforementioned values.

[0054] Specifically, the value of a includes, but is not limited to: 0, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.7, 0.8, or any two of the above.

[0055] Specifically, the value of b includes, but is not limited to: 0.5, 1, 1.3, 1.5, 1.7, 2, 2.3, 2.5, 2.8, 3, or any two of the foregoing.

[0056] Specifically, the values ​​of 7-2x-na+y include, but are not limited to: 5.2, 5.5, 5.9, 6.2, 6.5, 6.6, 6.7, 6.95, 7, 7.1 or any two of the above.

[0057] In addition, using appropriate M1 and / or Q elements can further improve the ionic conductivity of the compound, reduce interfacial impedance, and enhance cycling performance and rate performance.

[0058] In some embodiments, M1 includes one or more of Ba, Mg, Ca, and Sr. Further, M1 includes one or more of Ba, Mg, and Ca.

[0059] In some implementations, Q includes one or more of the elements Ta, Nb, W, Sb, Gd, Y, and Rb. Further, Q includes the element Ta.

[0060] Without restriction, the general formula is Li 7-2x-na+y Ga x La b M1 y Zr 2-a Q a O 12 The compounds include Li 6.5 Ga 0.1 La 2.8 Ba 0.2 Zr 1.6 Ta 0.4 O 12 Li 6.5 Ga 0.1 La 2.8 Mg 0.2 Zr 1.6 Ta 0.4 O 12 Li 6.5 Ga 0.1 La 2.8 Ca 0.2 Zr 1.6 Ta 0.4 O 12 Li 6.5 Ga 0.2 La 2.5 Ba 0.5 Zr 1.6 Ta 0.4 O 12 Li 6.5 Ga 0.1 La 2.8 Mg 0.2 Zr 1.6 Nb 0.4 O 12 Li 5.9 Ga 0.3 La 2.8 Mg 0.2 Zr 1.6 Nb0.4 O 12 Li 5.9 Ga 0.3 La 2.8 Mg 0.2 Zr 1.6 Ta 0.4 O 12 Li 6.6 Ga 0.2 La3Zr 1.6 Ta 0.4 O 12 Li 6.5 Ga 0.3 La 2.8 Ba 0.2 Zr2O 12 Li 5.2 Ga 0.8 La 2.8 Ca 0.2 Zr 1.6 Ta 0.4 O 12 Li 6.5 Ga 0.1 La 2.8 Ba 0.2 Zr 1.8 S 0.2 O 12 Li 6.5 Ga 0.1 La 2.8 Ba 0.2 Zr 1.6 W 0.4 O 12 Li 6.95 Ga 0.2 La 2.8 Ba 0.2 Zr 1.95 Ta 0.05 O 12 Li7Ga 0.2 La 2.8 Ba 0.2 Zr 1.9 Y 0.1 O 12 Japanese Li 7.1 Ga 0.2 La 2.8 Ba 0.2 Zr 1.9 Rb 0.1 O 12、 One kind or many kinds in the middle.

[0061] Among them, there is one small implementation method, the general method is Li. 7-2x-na+y Ga x La b M1y Zr 2-a Q a O 12 The compound is a garnet-type compound. Using a garnet-type compound can further improve the ionic conductivity of the compound, while also having good compatibility with lithium metal anodes, thus comprehensively improving cycle performance and rate performance.

[0062] In some embodiments, a metal layer is further disposed on the side of the second solid electrolyte membrane near the negative electrode. The introduction of the metal layer enables the formation of a metal-Li alloy when combined with the lithium metal negative electrode, reducing the interfacial impedance between the second solid electrolyte membrane and the lithium metal negative electrode, and improving cycle performance and rate performance. Further, the contact angle between the metal layer and the molten lithium metal is ≤20 degrees (°), and can be selected as 10° to 20°.

[0063] In some embodiments, the metal layer includes one or more of Au, Ag, and Zn elements.

[0064] In some embodiments, the thickness of the metal layer is 14 nanometers (nm) to 34 nm. Specifically, the thickness of the metal layer includes, but is not limited to, 14 nm, 16 nm, 18 nm, 20 nm, 24 nm, 28 nm, 30 nm, 34 nm, or any combination thereof.

[0065] In some embodiments, the solid-state battery further includes a third solid-state electrolyte membrane disposed between the positive electrode and the first solid-state electrolyte membrane. The materials of the third solid-state electrolyte membrane and the second solid-state electrolyte membrane each independently comprise materials of the general formula Li. 7-2x-na+y Ga x La b M1 y Zr 2-a Q a O 12 The compound of the above general formula can be incorporated between the positive electrode and the sulfide solid electrolyte to reduce side reactions between the positive electrode material and the sulfide solid electrolyte, thereby improving the cycle performance and rate performance of the battery.

[0066] Understandably, provided that the general formula structure is satisfied, the compound in the third solid electrolyte membrane may be the same as or different from the compound in the second solid electrolyte membrane.

[0067] In some embodiments, the thickness of the third solid electrolyte membrane is 0.1 mm to 0.7 mm. Specifically, the thickness of the third solid electrolyte membrane includes, but is not limited to, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, or any combination thereof.

[0068] In some embodiments, the thickness of the second solid electrolyte membrane is 0.1 mm to 0.7 mm. Specifically, the thickness of the second solid electrolyte membrane includes, but is not limited to, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, or any range between the two aforementioned.

[0069] In some embodiments, the thickness of the first solid electrolyte membrane is 0.9 mm to 1.4 mm. Specifically, the thickness of the first solid electrolyte membrane includes, but is not limited to, 0.9 mm, 1 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, or any range between the two aforementioned.

[0070] Without limitation, the sulfide solid electrolyte can be, for example, Li6PS5Cl, Li 5.5 PS 4.5 Cl 1.5 Li 5.7 PS 4.7 Cl 1.3 Li 6.2 PS 5.2 Cl 0.8 Li 6.4 PS 5.4 Cl 0.6 Li3PS4, Li 10 GeP2S 12 and Li 10 SnP2S 12 One or more of them.

[0071] In some embodiments, the positive electrode includes a positive active layer, the material of which includes a positive active material and a halide solid electrolyte. By introducing a halide solid electrolyte into the positive active layer, the contact between the positive active material and the sulfide solid electrolyte can be further reduced, thereby reducing the occurrence of side reactions.

[0072] In some embodiments, the halide solid electrolyte includes Li dM2Cl6, where M2 includes one or more metals from Group III and Group IV, with 2 ≤ d ≤ 3. Further, M2 includes one or more of In, Y, La, Sc, Er, Yb, Ho, Ti, Zr, and Hf. Using appropriate M2 elements can further improve the ionic conductivity of halide solid electrolytes, reduce interfacial impedance, and enhance cycle performance and rate performance.

[0073] Without limitation, the halide solid electrolyte includes Li3YCl6, Li3InCl6, Li3ErCl6, Li3YbCl6, Li2ZrCl6, and Li 2.4 Zr 0.6 Y 0.4 Cl6, Li 2.4 Zr 0.6 Er 0.4 Cl6 and Li 2.4 Zr 0.6 Ho 0.4 One or more of Cl6.

[0074] Without limitation, the halide solid electrolyte can be a commercially available product or can be synthesized in-house. In-house synthesis can be carried out via a mechanochemical method. Specifically, it may include the following steps:

[0075] The halide solid electrolyte was prepared by ball milling a mixture of lithium salt LiCl and metal halide of M2.

[0076] Without limitation, metal halides of M2 can include, for example, InCl3, YCl3, LaCl3, ScCl3, ErCl3, YbCl3, HoCl3, ZrCl4, HfCl4, etc.

[0077] Without limitation, the ball mill speed can be from 300 rpm to 700 rpm.

[0078] Without limitation, the mass ratio of zirconium beads to the mixture used in the ball mill is (15-50):1.

[0079] Without limitation, the ball milling time can be 5 hours (h) to 20 hours.

[0080] In some embodiments, the ball milling step is followed by annealing, with annealing conditions including a temperature of 120°C to 480°C and a time of 4 to 15 hours.

[0081] In some embodiments, the positive electrode active material may be a known positive electrode active material for batteries. As a non-limiting example, the positive electrode active material may include one or more of the following materials: lithium-containing phosphates with an olivine structure, lithium transition metal oxides, and their respective modified compounds. However, this application is not limited to these materials, and other conventional materials that can be used as positive electrode active materials for batteries may also be used. These positive electrode active materials may be used alone or in combination of two or more. Examples of lithium transition metal oxides include, but are not limited to, one or more of lithium cobalt oxides (such as LiCoO2), lithium nickel oxides, lithium manganese oxides, lithium nickel cobalt oxides, lithium manganese cobalt oxides, lithium nickel manganese oxides, lithium nickel cobalt manganese oxides, lithium nickel cobalt aluminum oxides, and their modified compounds. Non-limiting examples of lithium-containing phosphates with an olivine structure include, but are not limited to, one or more of lithium iron phosphate, lithium iron phosphate and carbon composites, lithium manganese phosphate, lithium manganese iron phosphate, and lithium manganese iron phosphate and carbon composites. Non-limiting examples of lithium cobalt oxides may include LiCoO2; non-limiting examples of lithium nickel oxides may include LiNiO2; non-limiting examples of lithium manganese oxides may include LiMnO2, LiMn2O4, etc.; non-limiting examples of lithium nickel cobalt manganese oxides may include LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2 (also known as NCM) 333 LiNi 0.5 Co 0.2 Mn 0.3 O2 (also known as NCM) 523 LiNi 0.5 Co 0.25 Mn 0.25 O2 (also known as NCM) 211 LiNi 0.6 Co 0.2 Mn 0.2 O2 (also known as NCM) 622 LiNi 0.8 Co 0.1 Mn 0.1 O2 (also known as NCM) 811 Examples of lithium nickel cobalt aluminum oxides include LiNi, etc. 0.8 Co 0.15 Al 0.05 O2.

[0082] In some embodiments, the solid-state battery is an all-solid-state battery.

[0083] Other embodiments of this application also provide a solid electrolyte material, including the general formula Li6.6-3x-a+yGa x La b M1 y Zr 2-a Q a O 12 The compounds are defined as follows: 0 < x ≤ 0.3, 0 ≤ y ≤ 0.5, 0 ≤ a ≤ 0.8, 0 ≤ b ≤ 3, M1 includes one or more of the main group II metal elements, and Q includes one or more of the main group I metal elements, the subgroup III metal elements, the main group V and subgroup V metal elements, and the main group VI and subgroup V metal elements; wherein 5.9 < 6.6 - 3x - a + y < 6.7.

[0084] It is understood that the above-mentioned solid electrolyte material has the same technical solution and advantages as the material of the second solid electrolyte membrane in the solid battery as described above, and will not be repeated here.

[0085] In some embodiments, the solid electrolyte material can be synthesized via a mechanochemical method. Without limitation, the synthesis method includes the following steps:

[0086] The solid electrolyte material is prepared by mixing an oxygen-containing lithium source and a metal source containing other metal elements in the general formula, ball milling, and sintering.

[0087] Without limitation, examples of oxygen-containing lithium sources include Li2CO3, Li2O, and LiNO3.

[0088] Without limitation, other metal sources can include, for example: La2O3, Ga2O3, Ga(NO3)3, ZrO2, Ta2O5, Ba(NO3)2, Ca(NO3)2, Mg(NO3)2, Nb2O5, W2O5, Sb2O3, Gd2O3, Y2O3, RbNO3, etc.

[0089] Without limitation, the rotational speed of the ball mill can be from 150 rpm to 250 rpm.

[0090] Without limitation, the milling media can be organic solvents, such as nonpolar solvents or protonated polar solvents like methanol, ethanol, propanol, toluene, p-xylene, trimethylbenzene, pseudotrimethylbenzene, n-heptane, and cyclohexane. The volume ratio of the organic solvent to the metal source of each metal element is (2-3):1.

[0091] Without limitation, the ball milling time can be 3 hours to 12 hours.

[0092] In some embodiments, the sintering step includes: pre-firing at 850°C to 950°C for 5 to 24 hours, followed by sintering at 1000°C to 1300°C for 5 to 12 hours. A forming process may also be included between the pre-firing and sintering steps, such as pressing at a pressure of 200 mPa to 400 mPa.

[0093] Other embodiments of this application also provide an electrical device, including a solid-state battery as described above or a solid-state electrolyte material as described above.

[0094] The solid-state battery and power device of this application will be described below with appropriate reference to the accompanying drawings.

[0095] Unless otherwise specified, the term "solid-state battery" as used in this application refers to a battery in which the electrolyte includes a solid electrolyte. Typically, a solid-state battery includes a positive electrode, a solid electrolyte layer, and a negative electrode. During charging and discharging, active ions repeatedly insert and extract between the positive and negative electrodes. The solid electrolyte layer serves to conduct ions between the positive and negative electrodes and also isolates them, thus preventing short circuits. Therefore, solid-state batteries do not require the separator found in traditional lithium-ion batteries.

[0096] In some embodiments, the positive electrode includes a positive current collector and a layer of positive active material disposed on at least one surface of the positive current collector.

[0097] Without limitation, the weight percentage of the positive electrode active material in the positive electrode active material layer can be ≥60wt%, and can be optionally 70wt% to 99wt%.

[0098] In some embodiments, the positive electrode active material layer further includes a positive electrode electrolyte material. Further, the positive electrode electrolyte material includes the halide solid electrolyte. Non-limitingly, the weight percentage of the positive electrode electrolyte material in the positive electrode active material layer can be from 1 wt% to 30 wt%.

[0099] In some embodiments, the positive electrode active material layer further includes a conductive agent (which may be referred to as a positive electrode conductive agent). As a non-limiting example, the positive electrode conductive agent may be a carbon conductive agent. Non-limitingly, the carbon conductive agent may include one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers. In some embodiments, the positive electrode conductive agent may include, but is not limited to, one or more of SP, KS-6, acetylene black, branched Ketjen black ECP, SFG-6, vapor-grown carbon fiber VGCF, carbon nanotubes (CNTs), and graphene. Non-limitingly, the weight percentage of the positive electrode conductive agent in the positive electrode active material layer may be 0–10 wt%, more further 0–8 wt%, even further 0–5 wt%, and even further 0.1 wt%–3 wt%. When the positive electrode material is prepared into a positive electrode active material layer using a dry method, the positive electrode conductive agent can be incorporated into the positive electrode material, thereby improving the conductivity of the positive electrode active material layer.

[0100] In some embodiments, the mass percentage of positive electrode active material, positive electrode electrolyte material and conductive agent in the positive electrode active material layer is (70% to 99%):(1% to 30%).

[0101] In some embodiments, the positive electrode active material layer optionally includes a binder (which may be referred to as a positive electrode binder). As a non-limiting example, the positive electrode binder may include one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a terpolymer of PVDF-tetrafluoroethylene-propylene, a terpolymer of PVDF-hexafluoropropylene-tetrafluoroethylene, a tetrafluoroethylene-hexafluoropropylene copolymer, and fluorinated acrylate resins. The aforementioned non-limiting examples of positive electrode binders are all organic binders and belong to organic components. Typically, the weight percentage of the positive electrode binder in the positive electrode active material layer can be 0–10 wt%, more commonly 0–8 wt%, even more commonly 0.1 wt%–5 wt%, and even more commonly 1 wt%–5 wt%. When the positive electrode material is formulated into a positive electrode slurry using a wet process and then the positive electrode active material layer is prepared, the positive electrode binder can be placed in the positive electrode slurry, which can assist in film formation and also promote the formation of a good electrical contact network between the active particles in the positive electrode active material layer.

[0102] Non-limiting, the positive electrode active material layer may include a positive electrode active material, a positive electrode electrolyte material, a positive electrode conductive agent, and a positive electrode binder. The types and contents of each component can be found in the context of this application.

[0103] As a non-limiting example, the positive current collector has two surfaces that are opposite to each other in its own thickness direction, and the positive active material layer is disposed on either or both of the two opposite surfaces of the positive current collector.

[0104] In some embodiments, the positive electrode current collector may be a metal foil or a composite current collector. For example, aluminum foil may be used as the metal foil. In the positive electrode current collector, the composite current collector may include a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. In the positive electrode current collector, the composite current collector may be obtained by forming a metal material on the polymer material substrate. Non-limiting examples of the metal material in the positive electrode current collector may include at least one of aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver, and silver alloy. Non-limiting examples of the polymer material substrate in the positive electrode current collector may include one or more of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), and polyethylene (PE).

[0105] In some embodiments, the positive electrode sheet can be prepared by: dry mixing the components used to prepare the positive electrode sheet, then heating and pressurizing the mixed material to knead it into a clump, hot rolling to form a self-supporting positive electrode sheet, and hot rolling to combine the self-supporting positive electrode sheet with a positive current collector. The self-supporting positive electrode sheet can be combined with at least one side (single or double sides) of the positive current collector to form a positive active layer, thereby obtaining the positive electrode sheet. Non-limitingly, a dual planetary mixer can be used for dry mixing. Non-limitingly, a kneading and heating process can be used. Non-limitingly, the temperature for hot rolling can be 75°C to 85°C, and further, such as 78°C, 80°C, 82°C, etc. The method of assembling solid-state batteries using the positive electrode sheet is suitable for industrial mass production.

[0106] In some embodiments, the positive electrode sheet can be prepared by dispersing the components used to prepare the positive electrode sheet, such as the positive electrode active material, the positive electrode electrolyte material, the positive electrode conductive agent, the positive electrode binder, and any other components, in an organic solvent to form a positive electrode slurry. Further, the positive electrode slurry is coated onto at least one surface of the positive electrode current collector, and after drying, cold pressing, and other processes, a positive electrode active layer is formed, thus obtaining the positive electrode sheet. Cold pressing can be performed using a cold rolling mill. Non-limitingly, the organic solvent in the positive electrode slurry can include one or more of p-xylene, trimethylbenzene, butyl butyrate, heptane, etc., and more specifically, p-xylene. The surface of the positive electrode current collector coated with the positive electrode slurry can be a single surface of the positive electrode current collector or both surfaces of the positive electrode current collector. The solid content (mass percentage) of the positive electrode slurry can be 40 wt% to 80 wt%. The viscosity of the positive electrode slurry at room temperature can be adjusted to 5000 mPa·s to 25000 mPa·s. When coating the positive electrode slurry, the coating density per unit area, measured by dry weight (excluding solvent), can be 15 mg / cm², based on the amount coated on one side of the positive electrode current collector. 2 )~35mg / cm2 However, this is not the only possibility. The compacted density of the positive electrode sheet can be 3.0 g / cm³. 3 ~3.6g / cm 3 3.3g / cm³ is an option. 3 ~3.5g / cm 3 .

[0107] In some embodiments, the positive electrode active material and the positive electrode electrolyte material can be mixed manually in a mortar and pestle or by ball milling or roller milling. The ball milling or roller milling speed is 200 rpm to 320 rpm, and the time is 20 min to 70 min.

[0108] In some embodiments, the negative electrode sheet includes a negative current collector and a negative active material layer disposed on at least one surface of the negative current collector, the negative active material layer including a negative active material.

[0109] Unless otherwise stated, the negative electrode active material layer in this application includes at least a negative electrode active material layer.

[0110] Unless otherwise stated in this application, the negative electrode active material layer includes at least a negative electrode active material.

[0111] Without limitation, the negative electrode active material layer may include a negative electrode electrolyte material.

[0112] In this application, unless otherwise specified, "negative electrode electrolyte material" refers to a solid electrolyte material that can be used in the negative electrode active material layer. The negative electrode electrolyte material can enhance the ion conductivity of the negative electrode active material layer, reduce interfacial impedance, and promote the efficient charge transfer between the negative electrode active material and the external environment, as well as the full release of its capacity.

[0113] In some embodiments, the negative electrode active material layer is a lithium metal film.

[0114] In some embodiments, the negative electrode sheet may include a negative current collector and a negative active material layer disposed on at least one surface of the negative current collector, the negative active material layer comprising a negative active substance. As a non-limiting example, the negative current collector has two surfaces opposite to each other in its own thickness direction, and the negative active material layer is disposed on either or both of the two opposite surfaces of the negative current collector.

[0115] In some embodiments, the negative electrode current collector may be a metal foil or a composite current collector. For example, copper foil may be used as the metal foil. In the negative electrode current collector, the composite current collector may include a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. In the negative electrode current collector, the composite current collector may be formed by forming a metal material on the polymer material substrate. Non-limiting examples of the metal material in the negative electrode current collector may include one or more of copper, copper alloys, nickel, nickel alloys, titanium, titanium alloys, silver, and silver alloys. Non-limiting examples of the polymer material substrate in the negative electrode current collector may include one or more of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), and polyethylene (PE).

[0116] In some embodiments, the solid-state battery may include an outer packaging. This outer packaging can be used to encapsulate the aforementioned solid-state battery cell.

[0117] In some embodiments, the outer packaging of a solid-state battery can be a rigid shell, such as a hard plastic shell, an aluminum shell, or a steel shell. The outer packaging of a solid-state battery can also be a soft pack, such as a pouch-type soft pack. The material of the soft pack can be plastic; further, non-limiting examples of plastics may include one or more of polypropylene, polybutylene terephthalate, and polybutylene succinate.

[0118] This application does not impose any particular limitation on the shape of the solid-state battery cell; it can be cylindrical, square, or any other arbitrary shape. For example, Figure 1 shows a square solid-state battery cell 5 as an example.

[0119] In some embodiments, referring to FIG2, the outer packaging may include a housing 51 and a cover plate 53. The housing 51 may include a base plate and side plates connected to the base plate, the base plate and side plates forming a receiving cavity. The housing 51 has an opening communicating with the receiving cavity, and the cover plate 53 can be placed over the opening to close the receiving cavity. A solid-state battery cell 52 is encapsulated within the receiving cavity. The number of solid-state battery cells 52 contained in the solid-state battery cell 5 may be one or more, which can be selected by those skilled in the art according to actual needs.

[0120] Solid-state batteries can be battery device 4 or battery pack 1.

[0121] The battery device includes at least one solid-state battery cell. The number of solid-state battery cells in the battery device can be one or more, and those skilled in the art can select an appropriate number according to the application and capacity of the battery device.

[0122] Figure 3 shows a battery device 4 as an example. Referring to Figure 3, in the battery device 4, multiple solid-state battery cells 5 can be arranged sequentially along the length of the battery device 4. Of course, they can also be arranged in any other arbitrary manner. Furthermore, the multiple solid-state battery cells 5 can be fixed in place by fasteners.

[0123] Optionally, the battery device 4 may also include a housing with a receiving space in which a plurality of solid-state battery cells 5 are housed.

[0124] In some embodiments, the battery devices described above can also be assembled into a battery pack, and the number of battery devices contained in the battery pack can be one or more. Those skilled in the art can select an appropriate number according to the application and capacity of the battery pack.

[0125] Figures 4 and 5 show a battery pack 1 as an example. Referring to Figures 4 and 5, the battery pack 1 may include a battery compartment and multiple battery devices 4 disposed within the battery compartment. The battery compartment includes an upper compartment 2 and a lower compartment 3, the upper compartment 2 covering the lower compartment 3 to form a closed space for accommodating the battery devices 4. The multiple battery devices 4 can be arranged in any manner within the battery compartment.

[0126] In a non-limiting sense, solid-state batteries can be used as a power source for electrical devices or as an energy storage unit for electrical devices. Electrical devices can include, but are not limited to, mobile devices, electric vehicles, electric trains, ships and satellites, energy storage systems, etc. Mobile devices can be, for example, mobile phones, laptops, etc.; electric vehicles can be, for example, pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, electric motorcycles, power tools, etc., but are not limited to these. This electrical device can also be applied to military equipment, aerospace, and other fields, and can also be applied to energy storage power systems such as hydroelectric, thermal, wind, and solar power plants.

[0127] As an electrical device, solid-state batteries can be selected based on its usage requirements.

[0128] Figure 6 shows an example of an electrical device 6. This electrical device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc. To meet the high power and high energy density requirements of this electrical device for solid-state batteries, a battery device or battery pack can be used.

[0129] Another example device could be a mobile phone, tablet, or laptop. These devices typically require a thin and light design and can use solid-state batteries as their power source.

[0130] To make the technical problems, technical solutions, and beneficial effects solved by this application clearer, the application will be further described in detail below with reference to embodiments and accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit this application or its applications. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0131] Where specific techniques or conditions are not specified in the examples, they shall be performed in accordance with the techniques or conditions described in the literature in this field or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0132] Example 1

[0133] 1) Preparation of positive electrode sheet

[0134] Positive electrode active material LiCoO2 and halide electrolyte Li3InCl6 were mixed at a mass ratio of 80%:20% to prepare positive electrode powder; the preparation method of halide electrolyte Li3InCl6 is as follows:

[0135] LiCl and InCl3 were mixed according to a general formula, ball-milled at 500 rpm for 5 hours, with a zirconium bead to mixture mass ratio of 30:1, to prepare a halide electrolyte. The mixture was then annealed at 320℃ for 10 hours.

[0136] 2) Preparation of negative electrode sheet

[0137] Li metal foil.

[0138] 3) Electrolyte membrane

[0139] The sulfide solid electrolyte Li6PS5Cl was selected, with a thickness of 1 mm.

[0140] 4) Oxide electrolyte membrane Li 6.5 Ga 0.1 La 2.8 Ba 0.2 Zr 1.6 Ta 0.4 O 12 The preparation method is as follows:

[0141] Li₂CO₃ is mixed with Ga₂O₃, La₂O₃, Ba(NO₃)₂, ZrO₂, and Ta₂O₅ according to the general formula Li 6.5 Ga 0.1 La 2.8 Ba0.2 Zr 1.6 Ta 0.4 O 12 The ingredients were mixed and ball-milled using isopropanol as the ball milling medium. The volume ratio of methanol to the mixture was 2:1, the rotation speed was 200 rpm, and the time was 6 hours. After ball milling, the mixture was dried in a vacuum oven.

[0142] The dried material was pre-fired at 900℃ for 12 hours to obtain coarse powder of garnet oxide.

[0143] Garnet-type oxide coarse powder was pressed into sheets under a pressure of 250 mPa and sintered at 1200℃ for 8 h to obtain an oxide electrolyte membrane with a thickness of 0.5 mm. XRD analysis of the oxide electrolyte membrane revealed that the synthesized oxide phase was a cubic phase of Ia-sd. SEM analysis showed that the oxide did not exhibit obvious grain boundaries, and the relative density reached 94.6%–97.2% (Figure 7).

[0144] 5) Fabrication of all-solid-state batteries

[0145] First, add about 100 mg of sulfide solid electrolyte Li6PS5Cl to the mold, and then compact the sulfide electrolyte powder with a pressure of 125 MPa to form an electrolyte film.

[0146] Take an oxide electrolyte membrane and plate it with gold on the side facing the lithium metal foil to form a coating (14 nm thick). Melt lithium metal onto the surface of the gold-plated coating of the oxide electrolyte membrane and add it to one side of the electrolyte membrane. Take another oxide electrolyte membrane and place it on the other side of the electrolyte membrane. Add positive electrode powder to the surface of the oxide electrolyte membrane opposite to the electrolyte membrane. Compact the whole structure with a pressure of 250 MPa to prepare an all-solid-state battery.

[0147] The preparation method of the solid-state battery in Example 2 is the same as that in Example 1, the main difference being that in step 4), Li2CO3 is mixed with Ga2O3, La2O3, Mg(NO3)2, ZrO2, and Ta2O5 according to the general formula Li 6.5 Ga 0.1 La 2.8 Mg 0.2 Zr 1.6 Ta 0.4 O 12 The ingredients were mixed and ball-milled to prepare Li oxide electrolyte membranes. 6.5 Ga 0.1 La 2.8 Mg 0.2 Zr 1.6 Ta 0.4 O 12.

[0148] The solid-state battery in Example 3 is prepared using the same method as in Example 1, the main difference being that in step 4), Li2CO3 is mixed with Ga2O3, La2O3, Ca(NO3)2, ZrO2, and Ta2O5 according to the general formula Li 6.5 Ga 0.1 La 2.8 Ca 0.2 Zr 1.6 Ta 0.4 O 12 The ingredients were mixed and ball-milled to prepare Li oxide electrolyte membranes. 6.5 Ga 0.1 La 2.8 Ca 0.2 Zr 1.6 Ta 0.4 O 12 .

[0149] The solid-state battery in Example 4 is prepared using the same method as in Example 1, the main difference being that in step 4), Li2CO3 is mixed with Ga2O3, La2O3, Ba(NO3)2, ZrO2, and Ta2O5 according to the general formula Li 6.5 Ga 0.2 La 2.5 Ba 0.5 Zr 1.6 Ta 0.4 O 12 The ingredients were mixed and ball-milled to prepare Li oxide electrolyte membranes. 6.5 Ga 0.2 La 2.5 Ba 0.5 Zr 1.6 Ta 0.4 O 12 .

[0150] The solid-state battery in Example 5 is prepared using the same method as in Example 1, the main difference being that in step 4), Li2CO3 is mixed with Ga2O3, La2O3, Mg(NO3)2, ZrO2, and Nb2O5 according to the general formula Li 6.5 Ga 0.1 La 2.8 Mg 0.2 Zr 1.6 Nb 0.4 O 12 The ingredients were mixed and ball-milled to prepare Li oxide electrolyte membranes. 6.5 Ga 0.1 La 2.8 Mg 0.2 Zr 1.6 Nb 0.4 O 12 .

[0151] The solid-state battery in Example 6 is prepared using the same method as in Example 1, the main difference being that in step 4), Li2CO3 is mixed with Ga2O3, La2O3, Mg(NO3)2, ZrO2, and Nb2O5 according to the general formula Li 5.9 Ga 0.3 La 2.8 Mg 0.2 Zr 1.6 Nb 0.4 O 12 The ingredients were mixed and ball-milled to prepare Li oxide electrolyte membranes. 5.9 Ga 0.3 La 2.8 Mg 0.2 Zr 1.6 Nb 0.4 O 12 .

[0152] The solid-state battery in Example 7 is prepared using the same method as in Example 1, the main difference being that in step 4), Li2CO3 is mixed with Ga2O3, La2O3, Mg(NO3)2, ZrO2, and Ta2O5 according to the general formula Li 5.9 Ga 0.3 La 2.8 Mg 0.2 Zr 1.6 Ta 0.4 O 12 The ingredients were mixed and ball-milled to prepare Li oxide electrolyte membranes. 5.9 Ga 0.3 La 2.8 Mg 0.2 Zr 1.6 Ta 0.4 O 12 .

[0153] The solid-state battery in Example 8 is prepared using the same method as in Example 1, the main difference being that in step 4), Li2CO3 is mixed with Ga2O3, La2O3, ZrO2, and Ta2O5 according to the general formula Li 6.6 Ga 0.2 La3Zr 1.6 Ta 0.4 O 12 The ingredients were mixed and ball-milled to prepare Li oxide electrolyte membranes. 6.6 Ga 0.2 La3Zr 1.6 Ta 0.4 O 12 .

[0154] The solid-state battery in Example 9 is prepared using the same method as in Example 1, the main difference being that in step 4), Li2CO3 is mixed with Ga2O3, La2O3, Ba(NO3)2, and ZrO2 according to the general formula Li 6.5 Ga 0.3 La 2.8 Ba 0.2 Zr2O 12 The ingredients were mixed and ball-milled to prepare Li oxide electrolyte membranes. 6.5 Ga 0.3 La 2.8 Ba 0.2 Zr2O 12 .

[0155] The solid-state battery in Example 10 is prepared using the same method as in Example 1, the main difference being that in step 4), Li₂CO₃ is mixed with Ga₂O₃, La₂O₃, Ca(NO₃)₂, ZrO₂, and Ta₂O₅ according to the general formula Li 5.2 Ga 0.8 La 2.8 Ca 0.2 Zr 1.6 Ta 0.4 O 12 The ingredients were mixed and ball-milled to prepare Li oxide electrolyte membranes. 5.2 Ga 0.8 La 2.8 Ca 0.2 Zr 1.6 Ta 0.4 O 12 .

[0156] The solid-state battery in Example 11 is prepared using the same method as in Example 1, the main difference being that in step 4), Li2CO3 is mixed with Ga2O3, La2O3, Ba(NO3)2, ZrO2, and Sb2O3 according to the general formula Li 6.5 Ga 0.1 La 2.8 Ba 0.2 Zr 1.8 Sb 0.2 O 12 The ingredients were mixed and ball-milled to prepare Li oxide electrolyte membranes. 6.5 Ga 0.1 La 2.8 Ba 0.2 Zr 1.8 Sb 0.2 O 12 .

[0157] The solid-state battery in Example 12 is prepared using the same method as in Example 1, the main difference being that in step 4), Li2CO3 is mixed with Ga2O3, La2O3, Ba(NO3)2, ZrO2, and W2O5 according to the general formula Li 6.5 Ga 0.1 La 2.8 Ba 0.2 Zr 1.6 W 0.4 O 12 The ingredients were mixed and ball-milled to prepare Li oxide electrolyte membranes. 6.5 Ga 0.1 La 2.8 Ba 0.2 Zr 1.6 W 0.4 O 12 .

[0158] The solid-state battery in Example 13 is prepared using the same method as in Example 1, the main difference being that in step 4), Li2CO3 is mixed with Ga2O3, La2O3, Ba(NO3)2, ZrO2, and Ta2O5 according to the general formula Li 6.95 Ga 0.2 La 2.8 Ba 0.2 Zr 1.95 Ta 0.05 O 12 The ingredients were mixed and ball-milled to prepare Li oxide electrolyte membranes. 6.95 Ga 0.2 La 2.8 Ba 0.2 Zr 1.95 Ta 0.05 O 12 .

[0159] The solid-state battery in Example 14 is prepared using the same method as in Example 1, the main difference being that in step 4), Li2CO3 is mixed with Ga2O3, La2O3, Ba(NO3)2, ZrO2, and Y2O3 according to the general formula Li7Ga 0.2 La 2.8 Ba 0.2 Zr 1.9 Y 0.1 O 12 The ingredients were mixed and ball-milled to prepare the oxide electrolyte membrane Li7Ga. 0.2 La 2.8 Ba 0.2 Zr 1.9 Y 0.1 O 12 .

[0160] The solid-state battery in Example 15 is prepared using the same method as in Example 1, the main difference being that in step 4), Li2CO3 is mixed with Ga2O3, La2O3, Ba(NO3)2, ZrO2, and RbNO3 according to the general formula Li 7.1 Ga 0.2 La 2.8 Ba 0.2 Zr 1.9 Rb 0.1 O 12 The ingredients were mixed and ball-milled to prepare Li oxide electrolyte membranes. 7.1 Ga 0.2 La 2.8 Ba 0.2 Zr 1.9 Rb 0.1 O 12 .

[0161] The solid-state battery in Example 16 is prepared in the same way as in Example 1, except that the thickness of the oxide electrolyte membrane prepared in step 4) is 0.1 mm.

[0162] The solid-state battery in Comparative Example 1 was prepared using the same method as in Example 1, the main difference being that Li was used. 6.25 La3Al 0.25 Zr2O 12 Replacement oxide electrolyte membrane. Specifically, in step 4), Li₂CO₃ is reacted with La₂O₃, Al(NO₃)₃, and ZrO₂ according to the general formula Li 6.25 La3Al 0.25 Zr2O 12 The ingredients were mixed and ball-milled to prepare Li oxide electrolyte membranes. 6.25 La3Al 0.25 Zr2O 12 .

[0163] The solid-state battery in Comparative Example 2 was prepared using the same method as in Example 1, the main difference being that Li7La3Zr2O was used. 12 (Commercially available material LLZO) to replace oxide electrolyte membranes.

[0164] The main parameters of the examples and comparative examples are summarized in Table 1 below:

[0165] Table 1

[0166] The solid-state battery of Comparative Example 3 was prepared by the same method as that of Example 1, except that an oxide electrolyte membrane was not used.

[0167] Step 5) The preparation steps of the all-solid-state battery are as follows:

[0168] First, add about 100 mg of sulfide solid electrolyte Li6PS5Cl to the mold, and then compact the sulfide electrolyte powder with a pressure of 125 MPa to form an electrolyte film.

[0169] Positive electrode powder and Li-In alloy were added to both sides of the electrolyte membrane (using Li metal foil directly would result in too violent side reactions and make testing difficult), and the whole was compacted under a pressure of 500 MPa to prepare an all-solid-state battery.

[0170] Test example:

[0171] (1) Contact angle between lithium metal and oxide electrolyte membrane

[0172] Test method: Molten lithium metal is dropped onto the surface of an oxide electrolyte membrane, and the angle is measured after the image is taken by a high-resolution camera.

[0173] The test results are shown in Table 2 below:

[0174] Table 2

[0175] (2) Cyclic stability test

[0176] Test method: At 25℃, the solid-state battery cell was first charged to 4.3V at a current density of 0.1C (vs. Li). + / Li), the charging capacity at this point is recorded as the battery's first charge specific capacity. After resting for 10 minutes, it is discharged to 2.3V (vs. Li) at a current density of 0.1C. + / Li), the discharge capacity at this time is recorded as the first discharge specific capacity of the battery.

[0177] First-cycle coulombic efficiency (%) = First-cycle discharge specific capacity / First-cycle charge specific capacity × 100%.

[0178] The test results are shown in Table 3 below.

[0179] Table 3

[0180] (3) Rate performance test of solid-state batteries

[0181] Test method: At 25℃, the solid-state battery cell was first charged to 4.3V (vs. Li+ / Li) at a current density of 0.1C, left to stand for 10 minutes, and then discharged to 2.3V (vs. Li+ / Li) at a rate of 0.1C. The charge-discharge cycle was repeated 3 times. Then, the cell was charged and discharged 5 times at charge-discharge rates of 0.1C, 0.2C, 0.5C, 1C, and 2C respectively.

[0182] The test results are shown in Table 4 below.

[0183] Table 4

[0184] As can be seen, by using a specific general-form compound as the second solid electrolyte membrane in the lithium metal anode system, this application enables the battery to achieve better cycle performance and rate performance, while the lithium metal anode can achieve higher capacity.

[0185] Furthermore, by providing a metal layer on the surface of the second solid electrolyte membrane that contacts the lithium metal anode, it is beneficial to improve the contact interface between the two, thereby reducing the interfacial impedance between the second solid electrolyte membrane and the lithium metal anode.

[0186] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above 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.

[0187] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A solid-state battery, comprising a positive electrode, a first solid electrolyte membrane, a second solid electrolyte membrane, and a negative electrode, which are stacked sequentially; wherein the negative electrode is a lithium metal negative electrode; and the material of the first solid electrolyte membrane comprises a sulfide solid electrolyte. The material of the second solid electrolyte membrane includes Li 7-2x-na+y Ga x La b M1 y Zr 2-a Q a O 12 The compounds are defined as follows: 0 < x ≤ 0.3, 0 ≤ y ≤ 0.5, 0 ≤ a ≤ 0.8, 0 < b ≤ 3. M1 includes one or more of the main group II metal elements, and Q includes one or more of the main group I metal elements, the subgroup III metal elements, the main group V and subgroup V metal elements, and the main group VI and subgroup V metal elements. The valence of Q is V1, n = V1 - 4, -2 ≤ n ≤ 1, 5.2 ≤ 7 - 2x - na + y ≤ 7.

1.

2. The solid-state battery according to claim 1, wherein, It has one or two of the following characteristics: (1) M1 includes one or more of Ba, Mg, Ca and Sr elements; optionally, M1 includes one or more of Ba, Mg and Ca elements; (2) Q includes one or more of the following elements: Ta, Nb, W, Sb, Gd, Y, and Rb; Optionally, Q includes the Ta element.

3. The solid-state battery according to claim 1 or 2, wherein, The general formula is Li 7-2x-na+y Ga x La b M1 y Zr 2-a Q a O 12 The compound of is Li 6.5 Ga 0.1 La 2.8 Ba 0.2 Zr 1.6 Ta<\(0000020\)>O 12 、Li 6.5 Ga 0.1 La 2.8 Mg 0.2 Zr<\(0000026\)>Ta 0.4 O 12 、Li 6.5 Ga<\(0000030\)>La 2.8 Ca 0.2 Zr 1.6 Ta<\(0000034\)>O 12 、Li 6.5 Ga<\(0000037\)>La 2.5 Ba 0.5 Zr 1.6 Ta<\(0000041\)>O 12 、Li 6.5 Ga<\(0000044\)>La 2.8 Mg 0.2 Zr<\(0000047\)>Nb 0.4 O 12 、Li 5.9 Ga<\(0000051\)>La 2.8 Mg 0.2 Zr<\(0000054\)>Nb 0.4 O 12 、Li 5.9 Ga<\(0000058\)>La 2.8 Mg 0.2 Zr<\(0000061\)>Ta<\(0000062\)>[[ID=1{10}]]O 12 、Li 6.6 Ga 0.2 La3Zr 1.6 Ta 0.4 O 12 、Li 6.5 Ga<\(0000070\)>La 2.8 Ba 0.2 Zr2O Note: I assume the " 0.4 " and other similar tags are just placeholders and should be left as they are. If there's any specific rule for these tags that I'm missing, please let me know. Also, the line breaks are preserved as per the instruction. 12 , Li 5.2 , Ga 0.8 , La 2.8 , Ca 0.2 , Zr 1.6 , Ta 0.4 , O 12 , Li 6.5 , Ga 0.1 , La 2.8 , Ba 0.2 , Zr 1.8 , Sb 0.2 , O 12 , Li 6.5 , Ga 0.1 , La 2.8 , Ba 0.2 , Zr 1.6 , W 0.4 , O 12 , Li 6.95 , Ga 0.2 , La 2.8 , Ba 0.2 , Zr 1.95 , Ta 0.05 , O 12 , Li7Ga 0.2 , La 2.8 , Ba 0.2 , Zr 1.9 , Y 0.1 , O 12 , and Li 7.1 , Ga 0.2 , La 2.8 , Ba 0.2 , Zr 1.9 , Rb 0.1 , O 12、 or one or more of the following:

4. The solid-state battery according to any one of claims 1 to 3, wherein, The general formula is Li 7-2x-na+y Ga x La b M1 y Zr 2-a Q a O 12 The compound is a garnet-type compound.

5. The solid-state battery according to any one of claims 1 to 4, wherein, The second solid electrolyte membrane has a metal layer disposed on the side near the negative electrode sheet, and the metal layer has one or more of the following characteristics: (1) The metal layer includes one or more of Au, Ag and Zn elements; (2) The thickness of the metal layer is 14nm to 34nm.

6. The solid-state battery according to any one of claims 1 to 5, wherein, It also includes a third solid electrolyte membrane disposed between the positive electrode and the first solid electrolyte membrane; the third solid electrolyte membrane has one or both of the following characteristics: (1) The materials of the third solid electrolyte membrane and the second solid electrolyte membrane each independently include those with the general formula Li. 7-2x-na+y Ga x La b M1 y Zr 2-a Q a O 12 Compounds; (2) The thickness of the third solid electrolyte membrane is 0.1 mm to 0.7 mm.

7. The solid-state battery according to any one of claims 1 to 6, wherein, It has one or two of the following characteristics: (1) The thickness of the first solid electrolyte membrane is 0.9 mm to 1.4 mm; (2) The thickness of the second solid electrolyte membrane is 0.1 mm to 0.7 mm.

8. The solid-state battery according to any one of claims 1 to 7, wherein, The positive electrode includes a positive active layer, and the material of the positive active layer includes a positive active material and a halide solid electrolyte.

9. The solid-state battery according to claim 8, wherein, The halide solid electrolyte includes Li3M2Cl6, where M2 includes one or more of Group III main and transition metal elements; Optionally, M2 includes one or more of the following elements: In, Y, La, Sc, Er, Yb, and Ho.

10. A solid electrolyte material, comprising Li 7-2x-na+y Ga x La b M1 y Zr 2-a Q a O 12 The compounds are defined as follows: 0 < x ≤ 0.3, 0 ≤ y ≤ 0.5, 0 ≤ a ≤ 0.8, 0 < b ≤ 3. M1 includes one or more of the main group II metal elements, and Q includes one or more of the main group I metal elements, the subgroup III metal elements, the main group V and subgroup V metal elements, and the main group VI and subgroup V metal elements. The valence of Q is V1, n = V1 - 4, -2 ≤ n ≤ 1, 5.2 ≤ 7 - 2x - na + y ≤ 7.

1.

11. The solid electrolyte material according to claim 10, wherein, The solid electrolyte material is the material of the second solid electrolyte membrane in the solid battery according to any one of claims 2 to 4.

12. An electrical device comprising a solid-state battery according to any one of claims 1 to 9 or a solid-state electrolyte material according to any one of claims 10 to 11.

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