All-solid-state batteries and their applications

Abstract

This document provides all-solid-state batteries and their applications. [Solution] The all-solid-state battery is placed on the positive electrode side and has an ionic conductivity of 1 × 10⁻⁶ -4 S / cm~1×10 -2 The first solid electrolyte layer has a density of S / cm, and the negative electrode side has an ionic conductivity of 1 × 10⁻¹⁰. -3 S / cm~2×10 -2 The invention provides for an all-solid-state battery and its applications, which enable the solid electrolyte membrane in the all-solid-state battery to simultaneously satisfy high lithium-ion conductivity, excellent electrochemical oxidation-reduction stability, and excellent compatibility with the positive and negative electrodes, thereby improving the performance of the all-solid-state battery.

Description

[Technical Field]

[0001] This application relates to the field of battery technology, and more particularly to all-solid-state batteries and their applications. [Background technology]

[0002] With the rapid development of electric vehicles and wearable devices, the demand for high-performance lithium-ion batteries is increasing. Among these, all-solid-state batteries are attracting widespread attention as a type of lithium-ion battery due to their advantages of high energy density, superior safety, and strong durability. However, in the practical application of all-solid-state batteries, it is difficult for the solid electrolyte membrane to simultaneously satisfy excellent film formation properties, high lithium-ion conductivity, excellent electrochemical oxidation-reduction stability, and excellent compatibility with the positive and negative electrodes, which limits the development and application of all-solid-state batteries. [Overview of the Initiative] [Problems that the invention aims to solve]

[0003] This invention proposes an all-solid-state battery and its applications. The all-solid-state battery and its applications provided by this invention enable the solid electrolyte membrane in the all-solid-state battery to simultaneously satisfy high lithium-ion conductivity, excellent electrochemical oxidation-reduction stability, and excellent compatibility with the positive and negative electrodes, thereby improving the performance of the all-solid-state battery. [Means for solving the problem]

[0004] To solve the above technical problems, the present invention provides the following all-solid-state battery. It is placed on the positive electrode side and has an ionic conductivity of 1 × 10⁻⁶. -4 S / cm~1×10 -2 A first solid electrolyte layer with a density of S / cm, It is placed on the negative electrode side and has an ionic conductivity of 1 × 10⁻⁶. -3 S / cm~2×10 -2 A second solid electrolyte layer with a density of S / cm, A solid-state battery comprising at least [a specific component].

[0005] In one embodiment of the present invention, the first solid electrolyte layer contains a first electrolyte, and the chemical formula of the first electrolyte is Li 2+n Zr 1-n M n Cl 6-x-y Br x I y where 0 ≤ n ≤ 0.6, 0 ≤ x ≤ 6, 0 ≤ y ≤ 6, and x + y ≤ 6, and M is selected from at least one of V, Cr, Mn, Fe, Co, or Ni.

[0006] In one embodiment of the present invention, M is Fe, and the value range of n is 0.01 ≤ n ≤ 0.5.

[0007] In one embodiment of the present invention, the second solid electrolyte layer contains a second electrolyte, and the chemical formula of the second electrolyte is Li a P 1-b T b S c O d X e where 5 < a < 6, 0 < b < 1, 1.5 < c < 5, 0 < d < 2.5, 4 < c + d < 5, and 1 < e < 2, T is selected from at least one of Al, Ga, In, Ti, Sc, As, Sb, Bi, V, or Nb, and X is selected from at least one of Cl, Br, or I.

[0008] In one embodiment of the present invention, T is selected from at least one of Sb, In, or Bi, X is Cl, and the value range of b is 0 < b ≤ 0.1.

[0009] In one embodiment of the present invention, the second solid electrolyte layer contains a second electrolyte, and the chemical formula of the second electrolyte is Li f P 1-g E g S w O g Q z where 5 < f < 10, 0 < g < 1, 3 < w < 6, 4 < w + g < 6, and 0 < z < 2, E is selected from at least one of Mg, Ca, Sr, Ba, Zn, Cr, Sn, or Pb, and Q is selected from at least one of Cl, Br, or I.

[0010] In one embodiment of the present invention, E is Mg, Q is Cl, and the range of the value of g is 0.01 ≤ g ≤ 0.1.

[0011] In one embodiment of the present invention, the thickness of the first solid electrolyte layer is 1 μm to 100 μm.

[0012] In one embodiment of the present invention, the thickness of the second solid electrolyte layer is 5 μm to 150 μm.

[0013] The present invention also provides electronic devices including the above-mentioned all-solid-state battery. [Effects of the Invention]

[0014] In summary, this invention proposes an all-solid-state battery and its applications. The solid electrolyte membrane in the all-solid-state battery has the advantage of high lithium-ion conductivity, which can improve the battery's operating efficiency. The electrochemical oxidation-reduction stability of the solid electrolyte membrane can be improved, allowing the electrolyte to effectively counteract problems such as oxidation-reduction reactions and instability at the electrode interface. By widening the potential window of the solid electrolyte membrane, the solid electrolyte membrane can be adapted to high-pressure cathodes such as lithium manganese oxide and lithium nickel manganese oxide, thereby improving the stability of the lithium-ion battery. Furthermore, the cycle performance of the all-solid-state battery can be improved, extending the battery's lifespan.

[0015] To more clearly illustrate the technical concepts of the embodiments of the present invention, the drawings necessary for describing the embodiments are briefly introduced below. Clearly, the drawings in the following description represent only a few embodiments of the present invention, and those skilled in the art can obtain other drawings based on these without expending any creative effort. [Brief explanation of the drawing]

[0016] [Figure 1] This is a structural diagram of an all-solid-state battery in one embodiment of the present invention. [Figure 2] This is a schematic diagram of the manufacturing process for the first solid electrolyte layer and the second solid electrolyte layer in one embodiment of the present invention. [Figure 3] This is a scanning electron microscope image of a solid electrolyte membrane in one embodiment of the present invention. [Figure 4] This figure shows the results of a room-temperature cycle performance test of an all-solid-state battery in Example 2 of the present invention. [Modes for carrying out the invention]

[0017] Embodiments of the present invention will be described below through specific examples, and those skilled in the art will readily understand other advantages and effects of the present invention from the disclosure herein. The present invention can also be carried out or applied by different specific embodiments, and each detail herein can be modified or altered in various ways without departing from the spirit of the invention, based on different viewpoints and applications.

[0018] It should be understood that the present invention can be carried out in different forms and should not be construed as being limited to the embodiments proposed herein. On the contrary, by providing these embodiments, the disclosure becomes thorough and complete, and the scope of the invention can be fully conveyed to those skilled in the art.

[0019] The technical proposal of the present invention will be described in more detail below by combining examples, and it is clear that the examples described are only a selection of examples of the present invention, not all examples. All other examples that a person skilled in the art could obtain without creative work based on the examples of the present invention are within the scope of the protection of the present invention.

[0020] Referring to Figure 1, the present invention proposes an all-solid-state battery 10, which includes, for example, a positive electrode 11, a negative electrode 12, and a solid electrolyte membrane 13, the solid electrolyte membrane 13 being positioned between the positive electrode 11 and the negative electrode 12, and the solid electrolyte membrane 13 includes, for example, a first solid electrolyte layer 131 and a second solid electrolyte layer 132 arranged in a stack, with the first solid electrolyte layer 131 positioned on the positive electrode 11 side and the second solid electrolyte layer 132 positioned on the negative electrode 12 side. In the all-solid-state battery 10 provided by the present invention, the solid electrolyte membrane 13 simultaneously satisfies the advantages of high lithium-ion conductivity, excellent electrochemical oxidation-reduction stability, and favorable compatibility with positive and negative electrodes, improving the battery's cycle performance, stability, and safety. Specifically, the first solid electrolyte layer 131 enables the solid electrolyte membrane 13 to be compatible with a high-voltage positive electrode, and the second solid electrolyte layer 132 can provide high lithium-ion conductivity and excellent electrochemical oxidation-reduction stability. In the present invention, the all-solid-state battery 10 is, for example, a primary battery or a secondary battery, and the secondary battery is, for example, a soft pack battery, a hard shell battery, or a cylindrical battery, and the present invention does not particularly limit the type or type of all-solid-state battery 10.

[0021] Referring to Figure 1, in one embodiment of the present invention, the positive electrode 11 includes, for example, a positive electrode active material, a solid electrolyte, a conductive agent, and a binder. Here, the positive electrode active material is at least one selected from, for example, lithium nickel cobalt manganese oxide (NCM), lithium nickel oxide (LNO), lithium manganese oxide (LMO), lithium nickel manganese oxide (LNMO), lithium cobalt oxide (LCO), or lithium nickel cobalt aluminum oxide (NCA), and the solid electrolyte is, for example, a halogen electrolyte that does not undergo an exothermic reaction with the positive electrode active material, thereby enhancing the safety of the battery. The conductive agent is at least one selected from, for example, conductive carbon (Super P), nanocarbon fiber (Vapor-grown carbon fiber, VGCF), acetylene black, carbon nanotube, or graphene. The binder is at least one selected from, for example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyethylene oxide, polyamide, polyacrylonitrile, polyacrylate, polyvinyl ether, polymethyl methacrylate, ethylene-propylene-diene ternary copolymer, polyhexafluoropropylene, or styrene-butadiene rubber. Herein, the present invention does not limit the mass ratio of the positive electrode active material, solid electrolyte, conductive agent, and binder, and can be selected according to actual requirements.

[0022] Referring to Figure 1, in one embodiment of the present invention, the positive electrode active material is, for example, LiNi 0.8 Co 0.1 Mn 0.1 O2 is a halogen electrolyte, and its chemical formula is, for example, Li 2.35 Zr 0.65 Fe 0.35 Cl5Br 0.5 I 0.5The conductive agent includes, for example, Super P and VGCF, with a mass ratio of Super P to VGCF being, for example, 1:1, and the binder is, for example, PTFE. The positive electrode active material, halogen solid electrolyte, conductive agent, and binder are uniformly mixed in, for example, a mass ratio of 69:29:1:1, and then the positive electrode 11 is obtained by dry pressing.

[0023] Referring to Figure 1, in one embodiment of the present invention, the material of the negative electrode 12 is selected from, for example, at least one of metallic lithium negative electrode material, carbon-based negative electrode material, or oxide negative electrode material, where the carbon-based negative electrode material includes, for example, carbon-based, silicon-based, or tin-based materials, and the oxide negative electrode material includes, for example, metal oxides, metal matrix composite oxides, and other oxides. In this embodiment, the negative electrode 12 is, for example, metallic lithium.

[0024] Referring to Figure 1, in one embodiment of the present invention, the thickness of the solid electrolyte membrane 13 is, for example, 5 μm to 200 μm, and the ionic conductivity is, for example, 1 × 10⁻¹⁶ -4 S / cm~2×10 -2 The coefficient of conductivity is S / cm. Here, the thickness of the first solid electrolyte layer 131 is, for example, 1 μm to 100 μm, and the ionic conductivity is, for example, 1 × 10⁻⁶. -4 S / cm~1×10 -2 The conductivity is S / cm, the thickness of the second solid electrolyte layer 132 is, for example, 5 μm to 150 μm, and the ionic conductivity is, for example, 1 × 10⁻¹⁶. -3 S / cm~2×10 -2 The coefficient of friction is S / cm. By controlling the thickness of the solid electrolyte membrane 13, the first solid electrolyte layer 131, and the second solid electrolyte layer 132, the cycle performance of the all-solid-state battery 10 can be improved and the battery's lifespan extended.

[0025] Referring to Figure 1, in one embodiment of the present invention, the first solid electrolyte layer 131 includes a first electrolyte, the first electrolyte being, for example, a halide electrolyte, which can widen the potential window of the solid electrolyte membrane 13 and allow the solid electrolyte membrane 13 to be adapted to a high-pressure positive electrode. Specifically, the chemical formula of the first electrolyte is, for example, Li2+n Zr 1-n M n Cl 6-x-y Br x I y Here, 0≦n≦0.6, 0≦x≦6, 0≦y≦6, x+y≦6, and M is at least one selected from V, Cr, Mn, Fe, Co, or Ni, etc. Furthermore, M is, for example, Fe, and the range of n is 0.01≦n≦0.5, specifically, n is, for example, 0.35. By controlling the type of element M in the first electrolyte and the range of n, the chemical stability and lithium ion conductivity of the first solid electrolyte layer 131 can be increased.

[0026] Referring to Figures 1 and 2, in one embodiment of the present invention, when manufacturing the first solid electrolyte layer 131, first, under an atmosphere of an inert gas such as argon, the chemical formula Li of the first electrolyte is used. 2+n Zr 1-n M n Cl 6-x-y Br x I y Based on this, the Li source, Zr source, M source, Cl source, Br source, and I source are stoichiometrically homogeneous, and then, for example, the mixture is placed in a ball mill can and subjected to ball milling to obtain the first electrolyte. Here, the Li source is, for example, at least one selected from LiCl, LiBr, or LiI, the Zr source is, for example, ZrCl4, the M source is, for example, a chloride of M, the Cl source is, for example, at least one selected from the Li source, Zr source, or M source, the Br source and I source are, for example, derived from the Li source, the mass ratio of balls to material is, for example, (1~100):1, the ball milling time is, for example, 1h~72h, and the rotation speed is, for example, 100rpm~1500rpm. After obtaining the first electrolyte, the first solid electrolyte layer 131 is manufactured by, for example, a powder compression molding method, a wet coating method, or an electrostatic spraying method.

[0027] Referring to Figure 2, in one embodiment of the present invention, when the first solid electrolyte layer 131 is produced by powder compression molding, first, the first electrolyte and the first binder are, for example, shear-mixed at a low temperature to make them homogenized, then the temperature is rapidly raised and shear-mixed at a high temperature to obtain a mixed material, and then the mixed material is placed in a roll press and roll-pressed at a high temperature to obtain the first solid electrolyte layer 131. Here, the first binder is, for example, PTFE, ethylene-tetrafluoroethylene copolymer (ETFE), fluorinated ethylene propylene copolymer (FEP), perfluoroalkoxy resin (PFA), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride The first electrolyte is selected from at least one of the following: Fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer, or polyvinylidene fluoride-trifluorochloroethylene copolymer, the content of the first electrolyte in the mixed material is, for example, 95 wt% to 99.9 wt%, the content of the first binder in the mixed material is, for example, 0.1 wt% to 5 wt%, the low-temperature shear temperature is, for example, -30°C to 15°C, the high-temperature shear temperature is, for example, 20°C to 200°C, and the high-temperature roll press temperature is, for example, 20°C to 200°C.

[0028] Referring to Figure 1, in another embodiment of the present invention, when the first solid electrolyte layer 131 is manufactured by a wet coating method or an electrostatic spray method, first, the first electrolyte, the second binder, and the solvent are uniformly mixed to obtain a mixed component, then the mixed component is applied to a substrate by a wet coating method or an electrostatic spray method, and then the substrate to which the mixed component has been applied is dried at a high temperature and peeled off to obtain the first solid electrolyte layer 131.Here, the second binder is, for example, PVDF, carboxymethyl cellulose (CMC), polymerized styrene butadiene rubber (SBR), polyvinyl pyrrolidone (PVP), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), polyacrylic acid (PAA), polyurethane, polyvinyl alcohol (PVA), sodium alginate. The solvent is at least one selected from alginate (Alg), ethylene-propylene-diene monomer, styrene-butadiene rubber, polyvinylidene fluoride, fluororubber, β-cyclodextrin polymer (β-cyclodextrin, β-CDp), polyacrylate emulsion (LA132), PTFE, ETFE, FEP, PFA, PCTFE, ECTFE, polyvinylidene fluoride-hexafluoropropylene copolymer, or vinylidene fluoride-trifluorochloroethylene copolymer, etc., and the solvent is, for example, toluene, chlorobenzene, xylene, dimethyl carbonate, N-methylformamide, n-hex The first electrolyte in the mixed component is selected from, for example, 30°C to 250°C. The substrate is selected from, for example, polyethylene glycol terephthalate (PET) film, smooth aluminum foil, or release paper. The high-temperature drying temperature is, for example, 30°C to 250°C.

[0029] Referring to FIG. 1, in one embodiment of the present invention, the second solid electrolyte layer 132 contains a second electrolyte, and the second electrolyte is, for example, a sulfide electrolyte, and the lithium ion conductivity and electrochemical oxidation-reduction stability of the second solid electrolyte layer 132 and the solid electrolyte membrane 13 can be further improved. Specifically, the chemical formula of the second electrolyte is, for example, Li a P 1-b T b S c O d X e or Li f P 1-g E g S w O g Q z and the like, and is at least one selected therefrom. Here, in Li a P 1-b T b S c O d X e , 5 < a < 6, 0 < b < 1, 1.5 < c < 5, 0 < d < 2.5, 4 < c + d < 5, 1 < e < 2, T is at least one selected from Al, Ga, In, Ti, Sc, As, Sb, Bi, V, or Nb, etc., and X is at least one selected from Cl, Br, or I, etc. Further, T is, for example, at least one selected from Sb, In, or Bi, X is Cl, and the range of the value of b is, for example, 0 < b ≦ 0.1. More specifically, when M is, for example, a +5-valent element, b is, for example, 0.04, and when M is, for example, a +3-valent element, b is, for example, 0.02. By controlling the type of M element, the type of T element, and the range of the value of b in the second electrolyte, the cycle performance of the all-solid-state battery 10 can be improved and the service life of the battery can be extended. <00A0489> Referring to FIG. 1, in one embodiment of the present invention, the chemical formula of the second electrolyte is Li f P 1-g E g S w O g Q zWhen it is so, here, 5 < f < 10, 0 < g < 1, 3 < w < 6, 4 < w + g < 6, 0 < z < 2, E is at least one selected from, for example, Mg, Ca, Sr, Ba, Zn, Cr, Sn, Pb, etc., and Q is at least one selected from, for example, Cl, Br, I, etc. Further, E is, for example, Mg, Q is, for example, Cl, the range of the value of g is, for example, 0.01 ≦ g ≦ 0.1, and specifically, g is, for example, 0.02. By controlling the type of E element, the type of Q element, and the range of the value of g in the second electrolyte, the cycle performance of the all-solid-state battery 10 can be improved, and the service life of the battery can be extended.

[0031] Referring to FIG. 1, in one embodiment of the present invention, when manufacturing the second solid electrolyte layer 132, first, in an atmosphere of an inert gas such as argon, the chemical formula of the second electrolyte is Li a P 1-b T b S c O d X e or Li f P 1-g E g S w O g Q zBased on this, a Li source, P source, T source, S source, and X source, or a Li source, P source, E source, S source, and Q source are stoichiometrically homogeneous mixed, then, for example, placed in a ball mill can and subjected to ball milling to obtain a precursor powder, and then the precursor powder is annealed and sintered at high temperature to obtain a second electrolyte. Here, the Li source is at least one selected from, for example, Li2S, LiCl, LiBr, or LiI, the P source is, for example, P2S5, the T source is, for example, an oxide of T, the S source is at least one selected from, for example, a Li source or a P source, the X source is, for example, derived from the Li source, the E source is, for example, an oxide of E, the Q source is, for example, derived from the Li source, the mass ratio of balls to material is, for example, (1~100):1, the ball milling time is, for example, 1h~48h, the rotation speed is, for example, 50rpm~1500rpm, the sintering temperature is, for example, 400℃~600℃, and the sintering time is, for example, 1h~48h. After obtaining the second electrolyte, the second solid electrolyte layer 132 is manufactured by, for example, powder compression molding, wet coating, or electrostatic spraying. Here, the process for producing the second solid electrolyte layer 132 by powder compression molding, wet coating, or electrostatic spraying is the same as the process for producing the first solid electrolyte layer 131 by powder compression molding, wet coating, or electrostatic spraying, and will not be described in detail here.

[0032] Referring to Figure 1, in one embodiment of the present invention, when manufacturing the solid electrolyte membrane 13, the first solid electrolyte layer 131 and the second solid electrolyte layer 132 are roll-pressed to form a composite solid electrolyte membrane 13.

[0033] Referring to Figure 1, in one embodiment of the present invention, the positive electrode 11, solid electrolyte membrane 13, and negative electrode 12 are sequentially stacked, sealed, hot-pressed, and cold-pressed to assemble the all-solid-state battery 10.

[0034] The present invention will be described more specifically below with reference to examples, but these examples should not be construed as limiting. Appropriate modifications can be made within the scope consistent with the spirit of the invention, and all such modifications fall within the technical scope of the invention.

Example

[0035] Example 1 Manufacture of the first electrolyte: Under an argon atmosphere, 1.35 mol of LiCl, 0.5 mol of LiBr, 0.5 mol of LiI, 0.65 mol of ZrCl4, and 0.35 mol of FeCl3 are subjected to high-energy ball milling to obtain a 2.35 Zr 0.65 Fe 0.35 Cl5Br 0.5 I 0.5 electrolyte material.

[0036] Manufacture of the second electrolyte: Under an argon atmosphere, 2 mol of Li2S, 1.5 mol of LiCl, 0.48 mol of P2S5, and 0.02 mol of Sb2O5 are subjected to high-energy ball milling to obtain a precursor powder. After that, the precursor powder is sintered at 500 °C for 10 hours, and after cooling, a 5.5 P 0.96 Sb 0.04 S 4.40 O 0.10 Cl 1.5 electrolyte material is obtained. 5.5 P 0.96 Sb 0.04 S 4.40 O 0.10 Cl 1.5 electrolyte material.

[0037] Manufacture of the first solid electrolyte layer: The 2.35 Zr 0.65 Fe 0.35 Cl5Br 0.5 I 0.5 electrolyte material and PTFE are uniformly mixed at -20 °C at a mass ratio of 99:1, and then heated to 80 °C to fibrillate PTFE to obtain a 2.35 Zr 0.65 Fe 0.35 Cl5Br 0.5 I 0.5 &PTFE mixed material. Next, a 2.35 Zr 0.65 Fe 0.35 Cl5Br 0.5 I 0.5The PTFE mixed material is fed into a roll press machine, and at 80°C, the gap of the roll press machine is adjusted to roll-press the electrolyte membrane to a thickness of 5 μm, thereby producing the first solid electrolyte layer.

[0038] Manufacturing of the second solid electrolyte layer: Li 5.5 P 0.96 S 0.04 S 4.40 O 0.10 Cl 1.5 The electrolyte material and PTFE are uniformly mixed at -20°C in a mass ratio of 99:1, then the temperature is raised to 80°C and the mixture is mixed to fibrousize the PTFE, and the Li is added to the second solid electrolyte layer. 5.5 P 0.96 S 0.04 S 4.40 O 0.10 Cl 1.5 A PTFE mixed material is obtained. Next, Li 5.5 P 0.96 S 0.04 S 4.40 O 0.10 Cl 1.5 The PTFE mixed material is fed into a roll press machine, and at 80°C, the gap of the roll press machine is adjusted to roll-press the electrolyte membrane to a thickness of 5 μm, thereby producing a second solid electrolyte layer.

[0039] Manufacturing of solid electrolyte membranes: The first solid electrolyte layer and the second solid electrolyte layer are sequentially roll-pressed in a roll press machine and combined to form a solid electrolyte membrane.

[0040] Cathode manufacturing: The positive electrode active material is LiNi 0.8 Co 0.1 Mn 0.1 It is O2, and the chemical formula for the halogen solid electrolyte is Li 2.35 Zr 0.65 Fe 0.35 Cl5Br 0.5 I 0.5 The conductive agent comprises Super P and VGCF, with a mass ratio of Super P to VGCF being, for example, 1:1, and the binder being, for example, PTFE. The positive electrode active material, halogen solid electrolyte, conductive agent, and binder are uniformly mixed in a mass ratio of, for example, 69:29:1:1, and then the positive electrode is obtained by dry pressing.

[0041] Negative electrode selection: Select metallic lithium as the negative electrode.

[0042] Battery manufacturing: The positive electrode, solid electrolyte membrane, and negative electrode are sequentially stacked, sealed, hot-pressed, and cold-pressed to assemble an all-solid-state soft pack battery.

[0043] Example 2 The difference between this embodiment and Embodiment 1 is that the thickness of the second solid electrolyte layer is adjusted to 25 μm by adjusting the roll gap of the roll press machine.

[0044] Example 3 The difference between this embodiment and Embodiment 1 is that the thickness of the second solid electrolyte layer is adjusted to 50 μm by adjusting the roll gap of the roll press machine.

[0045] Example 4 The difference between this embodiment and Embodiment 1 is that the thickness of the second solid electrolyte layer is adjusted to 150 μm by adjusting the roll gap of the roll press machine.

[0046] Example 5 The difference between this embodiment and Embodiment 2 is that the thickness of the first solid electrolyte layer is adjusted to 1 μm by adjusting the roll gap of the roll press machine.

[0047] Example 6 The difference between this embodiment and Embodiment 2 is that the thickness of the first solid electrolyte layer is adjusted to 50 μm by adjusting the roll gap of the roll press machine.

[0048] Example 7 The difference between this embodiment and Embodiment 2 is that the thickness of the first solid electrolyte layer is adjusted to 100 μm by adjusting the roll gap of the roll press machine.

[0049] Example 8 The difference between this embodiment and Example 2 is that the chemical formula of the first solid electrolyte layer is Li 2.2 Zr 0.8 Fe 0.2Cl5Br 0.5 I 0.5 The raw materials are 1.2 mol of LiCl, 0.5 mol of LiBr, 0.5 mol of LiI, 0.8 mol of ZrCl4, and 0.2 mol of FeCl3.

[0050] Example 9 The difference between this embodiment and Example 2 is that the chemical formula of the first solid electrolyte layer is Li 2.6 Zr 0.4 Fe 0.6 Cl5Br 0.5 I 0.5 The raw materials are 1.6 mol of LiCl, 0.5 mol of LiBr, 0.5 mol of LiI, 0.4 mol of ZrCl4, and 0.6 mol of FeCl3.

[0051] Example 10 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.5 P 0.99 S 0.01 S 4.475 O 0.025 Cl 1.5 The raw materials are 2 mol of Li2S, 1.5 mol of LiCl, 0.495 mol of P2S5, and 0.05 mol of Sb2O5.

[0052] Example 11 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.5 P 0.94 S 0.06 S 4.35 O 0.15 Cl 1.5 The raw materials are 2 mol of Li2S, 1.5 mol of LiCl, 0.45 mol of P2S5, and 0.05 mol of Sb2O5.

[0053] Example 12 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.5 P 0.9 S 0.1 S 4.25 O 0.25 Cl 1.5The raw materials are 2 mol of Li2S, 1.5 mol of LiCl, 0.45 mol of P2S5, and 0.05 mol of Sb2O5.

[0054] Example 13 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.1 P 0.96 S 0.04 S4O 0.10 Cl 1.9 The raw materials are 1.6 mol of Li2S, 1.9 mol of LiCl, 0.48 mol of P2S5, and 0.02 mol of Sb2O5.

[0055] Example 14 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.9 P 0.96 S 0.04 S 4.80 O 0.10 Cl 1.1 The raw materials are 2.4 mol of Li2S, 1.1 mol of LiCl, 0.48 mol of P2S5, and 0.02 mol of Sb2O5.

[0056] Example 15 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.5 P 0.96 S 0.04 S 4.40 O 0.10 Cl 1.4 Br 0.1 The raw materials are 2 mol of Li2S, 1.4 mol of LiCl, 0.1 mol of LiBr, 0.48 mol of P2S5, and 0.02 mol of Sb2O5.

[0057] Example 16 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.5 P 0.96 S 0.04 S 4.40 O 0.10 Cl 1.3 Br 0.1 I0.1 The raw materials are 2 mol of Li2S, 1.3 mol of LiCl, 0.1 mol of LiBr, 0.1 mol of LiI, 0.48 mol of P2S5, and 0.02 mol of Sb2O5.

[0058] Example 17 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.52 P 0.99 In 0.01 S 4.485 O 0.015 Cl 1.5 The raw materials are 2.01 mol of Li2S, 1.5 mol of LiCl, 0.495 mol of P2S5, and 0.005 mol of In2O3.

[0059] Example 18 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.54 P 0.98 In 0.02 S 4.47 O 0.03 Cl 1.5 The raw materials are 2.02 mol of Li2S, 1.5 mol of LiCl, 0.49 mol of P2S5, and 0.01 mol of In2O3.

[0060] Example 19 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.62 P 0.94 In 0.06 S 4.41 O 0.09 Cl 1.5 The raw materials are 2.06 mol of Li2S, 1.5 mol of LiCl, 0.47 mol of P2S5, and 0.03 mol of In2O3.

[0061] Example 20 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.7 P 0.9 In 0.1 S 4.35 O 0.15 Cl 1.5The raw materials are 2.1 mol of Li2S, 1.5 mol of LiCl, 0.45 mol of P2S5, and 0.05 mol of In2O3.

[0062] Example 21 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.14 P 0.98 In 0.02 S 4.07 O 0.03 Cl 1.9 The raw materials are 1.62 mol of Li2S, 1.9 mol of LiCl, 0.49 mol of P2S5, and 0.01 mol of In2O3.

[0063] Example 22 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.94 P 0.98 In 0.02 S 4.87 O 0.03 Cl 1.1 The raw materials are 2.42 mol of Li2S, 1.1 mol of LiCl, 0.49 mol of P2S5, and 0.01 mol of In2O3.

[0064] Example 23 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.54 P 0.98 In 0.02 S 4.47 O 0.03 Cl 1.4 Br 0.1 The raw materials are 2.02 mol of Li2S, 1.4 mol of LiCl, 0.1 mol of LiBr, 0.49 mol of P2S5, and 0.01 mol of In2O3.

[0065] Example 24 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.54 P 0.98 In 0.02 S 4.47 O 0.03 Cl 1.3 Br0.1 I 0.1 The raw materials are 2.02 mol of Li2S, 1.3 mol of LiCl, 0.1 mol of LiBr, 0.1 mol of LiI, 0.49 mol of P2S5, and 0.01 mol of In2O3.

[0066] Example 25 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.52 P 0.99 Bi 0.01 S 4.485 O 0.015 Cl 1.5 The raw materials are 2.01 mol of Li2S, 1.5 mol of LiCl, 0.495 mol of P2S5, and 0.005 mol of Bi2O3.

[0067] Example 26 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.54 P 0.98 Bi 0.02 S 4.47 O 0.03 Cl 1.5 The raw materials are 2.02 mol of Li2S, 1.5 mol of LiCl, 0.49 mol of P2S5, and 0.01 mol of Bi2O3.

[0068] Example 27 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.62 P 0.94 Bi 0.06 S 4.41 O 0.09 Cl 1.5 The raw materials are 2.06 mol of Li2S, 1.5 mol of LiCl, 0.47 mol of P2S5, and 0.03 mol of Bi2O3.

[0069] Example 28 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.7 P 0.9 Bi 0.1 S 4.35 O 0.15Cl 1.5 The raw materials are 2.1 mol of Li2S, 1.5 mol of LiCl, 0.45 mol of P2S5, and 0.05 mol of Bi2O3.

[0070] Example 29 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.14 P 0.98 Bi 0.02 S 4.07 O 0.03 Cl 1.9 The raw materials are 1.62 mol of Li2S, 1.9 mol of LiCl, 0.49 mol of P2S5, and 0.01 mol of Bi2O3.

[0071] Example 30 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.94 P 0.98 Bi 0.02 S 4.87 O 0.03 Cl 1.1 The raw materials are 2.42 mol of Li2S, 1.1 mol of LiCl, 0.49 mol of P2S5, and 0.01 mol of Bi2O3.

[0072] Example 31 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.54 P 0.98 Bi 0.02 S 4.47 O 0.03 Cl 1.4 Br 0.1 The raw materials are 2.02 mol of Li2S, 1.4 mol of LiCl, 0.1 mol of LiBr, 0.49 mol of P2S5, and 0.01 mol of Bi2O3.

[0073] Example 32 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.54 P 0.98 Bi 0.02 S 4.47 O 0.03 Cl1.3 Br 0.1 I 0.1 The raw materials are 2.02 mol of Li2S, 1.3 mol of LiCl, 0.1 mol of LiBr, 0.1 mol of LiI, 0.49 mol of P2S5, and 0.01 mol of Bi2O3.

[0074] Example 33 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.53 P 0.99 Mg 0.01 S 4.49 O 0.01 Cl 1.5 The raw materials are 2.015 mol of Li2S, 1.5 mol of LiCl, 0.495 mol of P2S5, and 0.01 mol of MgO.

[0075] Example 34 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.56 P 0.98 Mg 0.02 S 4.48 O 0.02 Cl 1.5 The raw materials are 2.03 mol of Li2S, 1.5 mol of LiCl, 0.49 mol of P2S5, and 0.02 mol of MgO.

[0076] Example 35 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.68 P 0.94 Mg 0.06 S 4.44 O 0.06 Cl 1.5 The raw materials are 2.09 mol of Li2S, 1.5 mol of LiCl, 0.47 mol of P2S5, and 0.06 mol of MgO.

[0077] Example 36 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.8 P 0.9 Mg 0.1 S 4.48 O0.1 Cl 1.5 The raw materials are 2.15 mol of Li2S, 1.5 mol of LiCl, 0.45 mol of P2S5, and 0.1 mol of MgO.

[0078] Example 37 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.16 P 0.98 Mg 0.02 S 4.08 O 0.02 Cl 1.9 The raw materials are 1.83 mol of Li2S, 1.9 mol of LiCl, 0.49 mol of P2S5, and 0.02 mol of MgO.

[0079] Example 38 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 6.96 P 0.98 Mg 0.02 S 5.88 O 0.02 Cl 0.1 The raw materials are 3.43 mol of Li2S, 0.1 mol of LiCl, 0.49 mol of P2S5, and 0.02 mol of MgO.

[0080] Example 39 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.56 P 0.98 Mg 0.02 S 4.48 O 0.02 Cl 1.4 Br 0.1 The raw materials are 2.03 mol of Li2S, 1.4 mol of LiCl, 0.1 mol of LiBr, 0.49 mol of P2S5, and 0.02 mol of MgO.

[0081] Example 40 The difference between this example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.56 P 0.98 Mg 0.02 S 4.48 O 0.02 Cl1.3 Br 0.1 I 0.1 The raw materials are 2.03 mol of Li2S, 1.3 mol of LiCl, 0.1 mol of LiBr, 0.1 mol of LiI, 0.49 mol of P2S5, and 0.02 mol of MgO.

[0082] Example 41 The difference between this embodiment and Embodiment 2 is that ETFE is selected as the first binder in the manufacturing of the first and second solid electrolyte layers.

[0083] Example 42 The difference between this embodiment and Embodiment 2 is that PCTFE is selected as the first binder in the manufacturing of the first and second solid electrolyte layers.

[0084] Example 43 The difference between this embodiment and Embodiment 2 is that the first solid electrolyte layer and the second solid electrolyte layer are manufactured by a wet coating method.

[0085] Specifically, the manufacturing of the first solid electrolyte layer: Li 2.35 Zr 0.65 Fe 0.35 Cl5Br 0.5 I 0.5 The electrolyte material, SBR binder, and xylene solvent are uniformly mixed in a mass ratio of 49:1:50 to obtain a mixed component. The mixed component is scraped onto smooth aluminum foil using a 5 μm coating device and vacuum-dried at 80°C to obtain a 5 μm thick Li film. 2.35 Zr 0.65 Fe 0.35 Cl5Br 0.5 I 0.5 The first solid electrolyte layer is manufactured.

[0086] Manufacturing of the second solid electrolyte layer: Li 5.5 P 0.96 S 0.04 S 4.40 O 0.10 Cl 1.5The electrolyte material, SBR binder, and xylene solvent are uniformly mixed in a mass ratio of 49:1:50 to obtain a mixed component. The mixed component is scraped onto smooth aluminum foil using a 25 μm coating device and vacuum-dried at 80°C to obtain a 25 μm thick Li film. 5.5 P 0.96 S 0.04 S 4.40 O 0.10 Cl 1.5 A second solid electrolyte layer is manufactured.

[0087] Example 44 The difference between this embodiment and Example 43 is that PVDF is selected as the second binder in the manufacturing process of the first and second solid electrolyte layers.

[0088] Example 45 The difference between this embodiment and Example 43 is that PAA is selected as the second binder in the manufacturing process of the first and second solid electrolyte layers.

[0089] Comparative Example 1 The difference between this comparative example and Example 2 is that the chemical formula of the second solid electrolyte layer is Li 5.5 PS 4.5 Cl 1.5 The raw materials are 2 mol of Li2S, 1.5 mol of LiCl, and 0.5 mol of P2S5.

[0090] Comparative Example 2 The difference between this comparative example and Example 2 is that the solid electrolyte membrane contains only the first solid electrolyte layer.

[0091] Comparative Example 3 The difference between this comparative example and Example 2 is that the solid electrolyte membrane contains only the second solid electrolyte layer.

[0092] Comparative Example 4 The difference between this comparative example and Example 2 is that the roll gap of the roll press machine is adjusted to set the thickness of the first solid electrolyte layer to 5 μm and the thickness of the second solid electrolyte layer to 1 μm.

[0093] The composition and parameters of the first and second solid electrolyte layers in each example and comparative example are shown in Table 1.

[0094] Composition of the first solid electrolyte layer and the second solid electrolyte layer in Examples 1-45 and Comparative Examples 1-4 [Table 1] JPEG2026081132000003.jpg242160JPEG2026081132000004.jpg242160JPEG2026081132000005.jpg242160JPEG2026081132000006.jpg60160

[0095] In this invention, performance tests are performed on all-solid-state batteries manufactured using different solid electrolyte membranes from Examples 1 to 45 and Comparative Examples 1 to 4.

[0096] Referring to Figure 3, in one embodiment of the present invention, the morphology of the solid electrolyte membrane of Example 2 is observed using, for example, a scanning electron microscope. Here, the magnification of the scanning electron microscope is, for example, 10,000x. As can be seen from Figure 3, the first solid electrolyte layer and the second solid electrolyte layer manufactured by the powder compression molding method have excellent self-supporting properties and can stably exist between the positive electrode and the negative electrode, thereby allowing the solid electrolyte membrane to exhibit its performance more effectively.

[0097] Referring to Figure 4, in one embodiment of the present invention, for example, a room-temperature cycle performance test is performed on the all-solid-state battery of Example 3. Specifically, at 25°C, the all-solid-state battery is cyclically charged and discharged at a charge / discharge rate of 1C / 1C within a specified voltage range of 2.5V to 4.3V, and the capacity (CC) and coulombic efficiency (CE) at different cycle numbers are obtained. As can be seen from Figure 4, the tendency for the battery capacity to decay with increasing cycle number is relatively gradual, and there is no fluctuation in the battery's coulombic efficiency, which remains stable at approximately 100%, indicating that the battery has good cycle performance.

[0098] Referring to Table 2, in one embodiment of the present invention, for example, a room-temperature cycle stability test is performed on the all-solid-state batteries of Examples 1 to 45 and Comparative Examples 1 to 4. Specifically, at 25°C, the all-solid-state batteries are cyclically charged and discharged at a charge / discharge rate of 1C / 1C within a specified voltage range of 2.5V to 4.3V. The test is terminated when the battery capacity reaches 80% of the initial capacity (State of Health, SOH), and the number of room-temperature cycles of the battery is recorded. The recorded results are shown in Table 2.

[0099] Test results of all-solid-state batteries in Examples 1-45 and Comparative Examples 1-4 [Table 2] JPEG2026081132000008.jpg141160

[0100] Referring to Tables 1 and 2, and comparing Example 2, Comparative Example 2, and Comparative Example 3, it can be seen that when only the first solid electrolyte layer is used as the solid electrolyte membrane, the battery immediately short-circuits and shows almost no cycle performance. When only the second solid electrolyte layer is used as the solid electrolyte membrane, the number of cycles at room temperature is only 493. However, when the first and second solid electrolyte layers are combined to form a solid electrolyte membrane, the number of cycles at room temperature of the battery increases to 1394. This indicates that in a solid electrolyte membrane formed by laminating the first and second solid electrolyte layers, the first electrolyte of the first solid electrolyte layer can be adapted to the positive electrode, and the second electrolyte of the second solid electrolyte layer can provide high lithium-ion conductivity and excellent electrochemical oxidation-reduction stability, thereby improving the cycle performance of the battery.

[0101] As can be seen by referring to Tables 1 and 2 and comparing Examples 1-4 and Comparative Example 4, as the thickness of the second solid electrolyte layer increases from 5 μm to 150 μm, the number of cycles at room temperature initially increases gradually, and then gradually decreases. In other words, the battery's cycle performance initially improves, and then tends to decline. Furthermore, when the thickness of the second solid electrolyte layer becomes as thin as 1 μm, the battery short-circuits. Therefore, the battery's cycle performance can be improved by controlling the thickness of the second solid electrolyte layer.

[0102] As can be seen by referring to Tables 1 and 2 and comparing Example 2 with Examples 5-7, as the thickness of the first solid electrolyte layer increases from 1 μm to 100 μm, the number of room-temperature cycles of the battery initially increases gradually, and then gradually decreases. In other words, the battery's cycle performance initially improves, and then tends to decline. Therefore, the battery's cycle performance can be improved by controlling the thickness of the first solid electrolyte layer.

[0103] As can be seen by referring to Tables 1 and 2 and comparing Examples 2 with Examples 8-9, as the amount of Fe doping in the first solid electrolyte layer increases, the ionic conductivity of the first solid electrolyte layer increases first and then decreases, and at the same time, the number of room-temperature cycles of the battery gradually increases first and then gradually decreases, that is, the cycle performance of the battery improves first and then decreases. Therefore, the cycle performance of the battery can be improved by controlling the amount of M doping in the first electrolyte layer.

[0104] Referring to Tables 1 and 2, a comparison of Example 2 with Examples 10-12 shows that as the amount of Sb doping in the second electrolyte increases, the ionic conductivity of the second solid electrolyte layer gradually decreases, and the number of room-temperature cycles of the battery initially increases gradually, then gradually decreases; that is, the battery's cycle performance initially improves, and then tends to decline. Referring to Tables 1 and 2, a comparison of Examples 17-20 shows that as the amount of In doping in the second solid electrolyte layer increases, the ionic conductivity of the second solid electrolyte layer gradually decreases, and the number of room-temperature cycles of the battery initially increases gradually, then gradually decreases; that is, the battery's cycle performance initially improves, and then tends to decline. Referring to Tables 1 and 2, a comparison of Examples 25-28 shows that as the amount of Bi doping in the second solid electrolyte layer increases, the ionic conductivity of the second solid electrolyte layer gradually decreases, and the number of room-temperature cycles of the battery initially increases gradually, then gradually decreases; that is, the battery's cycle performance initially improves, and then tends to decline. Therefore, by controlling the amount of T element doping in the second solid electrolyte layer, the cycle performance of the battery can be improved.

[0105] As can be seen by referring to Tables 1 and 2 and comparing Examples 33 to 36, as the amount of Mg doping in the second solid electrolyte layer increases, the ionic conductivity of the second solid electrolyte layer gradually decreases, the number of room-temperature cycles of the battery gradually increases first, and then gradually decreases; in other words, the cycle performance of the battery improves first, and then tends to decline. Therefore, the cycle performance of the battery can be improved by controlling the amount of E doping in the second electrolyte layer.

[0106] As can be seen by referring to Tables 1 and 2 and comparing Examples 2, 13, 14, 18, 21, 22, 26, 29, 30, and 34, 37, 38, when the doping amounts of Sb, In, Bi, or Mg in the second solid electrolyte layer are the same, the number of room-temperature cycles of the battery is maximized when 1.5 Cl atoms are contained in one second electrolyte molecule. On the other hand, when the number of Cl atoms in one second electrolyte molecule exceeds 1.5 or is less than 1.5, the number of room-temperature cycles of the battery decreases, i.e., the battery's cycle performance deteriorates. Therefore, the cycle performance of the battery can be improved by controlling the doping amount of element X or Q in the second electrolyte layer.

[0107] As can be seen by referring to Tables 1 and 2 and comparing Examples 2, 15, 16, 18, 23, 24, 26, 31, 32, and 34, 39, 40, when the doping amounts of Sb, In, Bi, or Mg in the second solid electrolyte layer are the same, doping the second solid electrolyte layer with one or more types of Br or I elements reduces the ionic conductivity of the second solid electrolyte layer and also reduces the number of room-temperature cycles of the battery, i.e., the battery's cycle performance deteriorates. Therefore, the number of types of elements contained in X or Q in the second electrolyte layer can be controlled to improve the battery's cycle performance.

[0108] Referring to Tables 1 and 2, and comparing Examples 18, 26, 34, and Comparative Example 1, it can be seen that when the second solid electrolyte layer is not doped with Sb, In, Bi, or Mg, the ionic conductivity of the second solid electrolyte layer increases, but the battery quickly short-circuits and has almost no cycle performance. This demonstrates that the Sb, In, Bi, or Mg elements doped into the second solid electrolyte layer can significantly improve the battery's cycle performance. Therefore, the battery's cycle performance can be improved by controlling the type of T or E element in the second electrolyte layer.

[0109] As can be seen by referring to Tables 1 and 2 and comparing Examples 2, 41, and 42, the ionic conductivity of the first and second solid electrolyte layers differs because the first binder used in the manufacturing process of the first and second solid electrolyte layers is different, resulting in different battery cycle performance. Specifically, when PTFE is used as the first binder, the number of room-temperature cycles of the battery is the highest, meaning the battery has the best cycle performance.

[0110] As can be seen by referring to Tables 1 and 2 and comparing Examples 2 and 43-45, the manufacturing methods for the first and second solid electrolyte layers are different, resulting in different ionic conductivity of the first and second solid electrolyte layers and thus different battery cycle performance. Specifically, compared to the wet coating method, the first and second solid electrolyte layers manufactured by the powder compression molding method have the highest ionic conductivity, and the number of room-temperature cycles of the batteries assembled with them is also the highest, meaning they have the best cycle performance.

[0111] The present invention also provides an electronic device comprising at least one of the above-described all-solid-state batteries, the all-solid-state battery being used to supply power. Here, the electronic device may be a vehicle, a mobile phone, a portable device, a laptop computer, a ship, an aerospace device, an electric toy, and a power tool, etc. In one embodiment of the present invention, the vehicle is, for example, a new energy vehicle, which may be a pure electric vehicle, a hybrid vehicle, or an extended-range vehicle, etc. Aerospace device includes airplanes, rockets, space shuttles, and spacecraft, etc. Electric toys include stationary or mobile electric toys, for example, game consoles, electric car toys, electric boat toys, and electric airplane toys, etc. Power tools include metal cutting power tools, polishing power tools, assembly power tools, and railway power tools, for example, electric drills, electric grinders, electric wrenches, electric screwdrivers, electric hammers, impact drills, concrete vibrators, and electric planers, etc. Since the electronic device comprises the above-described all-solid-state battery, it has the advantages of the above-described all-solid-state battery, but a detailed explanation is omitted here. [Industrial applicability]

[0112] In summary, the present invention proposes an all-solid-state battery and its applications. By combining a first solid electrolyte layer and a second solid electrolyte layer, a high-pressure resistant heterogeneous self-supporting solid electrolyte membrane is manufactured. This solid electrolyte membrane has the advantage of high lithium-ion conductivity, improving the battery's operating efficiency. Furthermore, the electrochemical oxidation-reduction stability of the solid electrolyte membrane can be improved, allowing the electrolyte to effectively counteract problems such as oxidation-reduction reactions and electrode interface instability. In addition, by widening the potential window of the solid electrolyte membrane, the solid electrolyte membrane can be adapted to high-pressure cathodes such as lithium manganese oxide and lithium nickel manganese oxide, improving the stability of the lithium-ion battery. Moreover, the first and second solid electrolyte layers can improve the battery's cycle performance and extend its lifespan.

[0113] The above description is merely a description of preferred embodiments and the technical principles used in the present application. Those skilled in the art should understand that the scope of the invention disclosed herein is not limited to technical solutions consisting of specific combinations of the above-described technical features, but should also include other technical solutions formed by arbitrarily combining the above-described technical features or their equivalent features, for example, technical solutions formed by substituting the above-described features with (but not limited to) similar functional technical features disclosed herein.

[0114] Except for the technical features described in the specification, other technical features are known to those skilled in the art, and in order to emphasize the innovativeness of the present invention, other technical features will not be described in detail here. [Explanation of Symbols]

[0115] 110 All-solid-state battery 11 Positive electrode 12 Negative electrode 13 Solid electrolyte membrane 131 First solid electrolyte layer 132 Second solid electrolyte layer

Claims

1. All-solid-state battery, It is placed on the positive electrode side of the all-solid-state battery and has an ionic conductivity of 1 × 10⁻⁶ －４ S / cm ~ 1 x 10 －２ A first solid electrolyte layer with a density of S / cm, It is placed on the negative electrode side of the all-solid-state battery and has an ionic conductivity of 1 × 10⁻⁶ －３ S / cm ~ 2 x 10 －２ A second solid electrolyte layer with a density of S / cm, A solid-state battery characterized by containing at least [a certain element].

2. The first solid electrolyte layer contains a first electrolyte, and the chemical formula of the first electrolyte is Li ２＋ｎ Zr １－ｎ M ｎ Cl ６－ｘ－ｙ Br ｘ I ｙ where 0 ≦ n ≦ 0.6, 0 ≦ x ≦ 6, 0 ≦ y ≦ 6, x + y ≦ 6, and M is at least one selected from V, Cr, Mn, Fe, Co, or Ni. The all-solid-state battery according to claim 1

3. The all-solid-state battery according to claim 2, characterized in that M is Fe and the range of n is 0.01 ≤ n ≤ 0.

5.

4. The second solid electrolyte layer contains a second electrolyte, and the chemical formula of the second electrolyte is Li ａ P １－ｂ T ｂ S ｃ O ｄ X ｅ The all-solid-state battery according to claim 1, wherein 5 < a < 6, 0 < b < 1, 1.5 < c < 5, 0 < d < 2.5, 4 < c + d < 5, 1 < e < 2, T is at least one selected from Al, Ga, In, Ti, Sc, As, Sb, Bi, V, or Nb, and X is at least one selected from Cl, Br, or I.

5. The all-solid-state battery according to claim 4, characterized in that T is at least one selected from Sb, In, or Bi, X is Cl, and the range of b is 0 < b ≤ 0.

1.

6. The second solid electrolyte layer contains a second electrolyte, and the chemical formula of the second electrolyte is Li ｆ P １－ｇ E ｇ S ｗ O ｇ Q ｚ The all-solid-state battery according to claim 1, wherein 5 < f < 10, 0 < g < 1, 3 < w < 6, 4 < w + g < 6, 0 < z < 2, E is at least one selected from Mg, Ca, Sr, Ba, Zn, Cr, Sn, or Pb, and Q is at least one selected from Cl, Br, or I.

7. The all-solid-state battery according to claim 6, characterized in that E is Mg, Q is Cl, and the range of g is 0.01 ≤ g ≤ 0.

1.

8. The all-solid-state battery according to claim 1, characterized in that the thickness of the first solid electrolyte layer is 1 μm to 100 μm.

9. The all-solid-state battery according to claim 1, characterized in that the thickness of the second solid electrolyte layer is 5 μm to 150 μm.

10. An electronic device characterized by including an all-solid-state battery as described in any one of claims 1 to 9.

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