Solid electrolyte membrane and method for producing the same, solid battery, and power consumption device

Abstract

This application relates to a solid electrolyte membrane, a manufacturing method thereof, a solid-state battery, and a power consumption device. The solid electrolyte membrane includes a solid electrolyte material layer and a fiber material layer disposed within the solid electrolyte material layer, the solid electrolyte material layer including an inorganic ceramic solid electrolyte material, and the fiber material layer including ceramic fibers. The mechanical properties of the solid electrolyte membrane, particularly its fracture toughness, are excellent, thereby reducing the fracture of the membrane layer.

Description

[Technical Field]

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS] This application references Chinese patent application No. 2023104857075, filed on May 4, 2023, entitled "Solid electrolyte membrane and manufacturing method thereof, solid-state battery, and power consumption device," the entire contents of which are incorporated herein by reference.

[0002] The present application relates to the field of battery technology, and in particular to a solid electrolyte membrane and its manufacturing method, a solid-state battery, and a power consuming device. [Background technology]

[0003] In recent years, the application range of batteries has become increasingly broad, and batteries are widely used in energy storage power systems such as hydroelectric, thermal, wind, and solar power plants, as well as in multiple fields such as power tools, electric bicycles, electric motorcycles, electric vehicles, military equipment, and aerospace. With the progress of battery research, solid-state batteries have emerged and have been regarded in recent years as a battery that can succeed lithium-ion batteries. Solid-state lithium battery technology can significantly increase the energy density of lithium batteries by replacing the electrolyte with a solid electrolyte.

[0004] Currently, solid electrolytes are divided into polymer-based solid electrolytes and inorganic ceramic-based solid electrolytes, and the weak mechanical properties of inorganic ceramic-based solid electrolytes compared to polymer-based solid electrolytes are a major bottleneck in the application of such solid electrolytes. Summary of the Invention

[0005] Based on this, the present application provides a solid electrolyte membrane, a manufacturing method thereof, a solid-state battery, and a power consumption device, and the solid electrolyte membrane has good mechanical properties.

[0006] According to a first aspect of the present application, there is provided a solid electrolyte membrane, the solid electrolyte membrane including a solid electrolyte material layer and a fiber material layer disposed inside the solid electrolyte material layer, the solid electrolyte material layer including an inorganic ceramic solid electrolyte material, and the fiber material layer including ceramic fibers.

[0007] In some embodiments thereof, the ceramic fibers are distributed in a staggered pattern, and optionally the ceramic fibers form a mesh structure, and more optionally the mesh structure is woven, and more optionally the mesh structure is parallel to the surface of the solid electrolyte membrane that contacts the electrode plate.

[0008] In some of the embodiments, the surface porosity of the fibrous layer is between 50% and 90%, and optionally the surface porosity of the fibrous layer is between 65% and 75%.

[0009] In some embodiments thereof, the ceramic fibers include one or more of silicon carbide fibers, silicon nitride fibers, boron nitride fibers, alumina fibers, and silica fibers, and optionally, the ceramic fibers include one or more of silicon carbide fibers, alumina fibers, and silica fibers.

[0010] In some of the embodiments, the aspect ratio of the ceramic fibers is ≧5, and optionally the aspect ratio of the ceramic fibers is 5-100.

[0011] In some embodiments thereof, the inorganic ceramic solid electrolyte material comprises a lithium ion solid electrolyte material, a sodium ion solid electrolyte material, or a potassium ion solid electrolyte material.

[0012] In some embodiments, the solid electrolyte membrane has one or more of the following characteristics (1) to (3): (1) The fracture toughness of the solid electrolyte membrane is ≧0.25 MPa m 1 / 2and optionally, the fracture toughness of the solid electrolyte membrane is ≧0.3 MPa m 1 / 2 and (2) The surface resistance of the solid electrolyte membrane is ≦5 Ω cm 2 and optionally, the surface resistance of the solid electrolyte membrane is ≦2 Ω cm 2 and (3) The thickness of the solid electrolyte membrane is ≦80 μm, and optionally, the thickness of the solid electrolyte membrane is ≦60 μm.

[0013] According to a second aspect of the present application, there is provided a method for producing the solid electrolyte membrane according to the first aspect, the method comprising the steps of: employing ceramic fibers to fabricate the fiber material layer; and coating the inorganic ceramic solid electrolyte material on the surface of the fiber material layer and filling gaps in the fiber material layer with the inorganic ceramic solid electrolyte material, and then forming the inorganic ceramic solid electrolyte material to produce the solid electrolyte membrane.

[0014] In some embodiments thereof, the step of producing the textile layer comprises: The method includes a step of forming the fiber material layer by distributing the ceramic fibers in a staggered pattern, and optionally, the ceramic fibers form a mesh structure, and more optionally, the mesh structure is formed by knitting, and more optionally, the mesh structure is parallel to the surface of the solid electrolyte membrane that contacts the electrode plate.

[0015] In some embodiments thereof, the step of fabricating the solid electrolyte membrane comprises: mixing the inorganic ceramic solid electrolyte material, an adhesive and a solvent to prepare an electrolyte slurry, or preparing an electrolyte powder from the inorganic ceramic solid electrolyte material; and coating and filling the electrolyte slurry or powder.

[0016] In some embodiments thereof, the adhesive comprises one or more of nitrile rubber (NBR), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyimide (PI), polyacrylonitrile (PAN), polyurethane (PU), polycarboxymethyl cellulose (CMC), cyclodextrin (CD), sodium alginate (SA), polysaccharide, and styrene butadiene rubber (SBR).

[0017] In some of the embodiments, the molding step includes one or two of drying and pressing, and optionally, the pressure of the pressing is 10 MPa to 600 MPa.

[0018] According to a third aspect of the present application, there is provided a solid-state battery, the solid-state battery including the solid electrolyte membrane according to the first aspect.

[0019] According to a fourth aspect of the present application, there is provided a power consuming device, the power consuming device comprising the solid-state battery according to the third aspect.

[0020] The above-mentioned solid electrolyte membrane has a fiber material layer containing ceramic fibers disposed inside the solid electrolyte material layer, which can exert a better fiber toughening effect when defects and fractures occur in the solid electrolyte membrane, thereby improving the mechanical properties of the solid electrolyte membrane, particularly the fracture toughness. [Brief explanation of the drawings]

[0021] In order to more clearly explain the technical solutions of the embodiments of the present application, the following briefly introduces the drawings that need to be used in the embodiments of the present application. It is obvious that the drawings described below are only some embodiments of the present application, and those skilled in the art can obtain other drawings based on the drawings without any creative efforts. [Figure 1] 1 is a schematic diagram of a solid-state battery according to an embodiment of the present application; [Figure 2]1 is a schematic diagram of a battery module according to an embodiment of the present application; [Figure 3] 1 is a schematic diagram of a battery pack according to an embodiment of the present application; [Figure 4] FIG. 4 is an exploded view of the battery pack shown in FIG. 3 according to the embodiment of the present application. [Figure 5] 1 is a schematic diagram of a power consuming device that uses a solid-state battery as a power source according to an embodiment of the present application. [Figure 6] FIG. 2 is a structural diagram of a fiber material layer located inside a solid electrolyte material layer in an embodiment of the present application. DETAILED DESCRIPTION OF THE INVENTION

[0022] Hereinafter, with appropriate reference to the drawings, embodiments specifically disclosing the solid electrolyte membrane and its manufacturing method, solid-state battery, and power consumption device of the present application will be described in detail. However, unnecessary detailed description may be omitted. For example, detailed description of well-known matters and redundant description of actually identical structures may be omitted. This is to avoid the following description becoming unnecessarily long and to facilitate understanding by those skilled in the art. Note that the drawings and the following description are provided to enable those skilled in the art to fully understand the present application and are not intended to limit the subject matter described in the claims.

[0023] The "ranges" disclosed in this application are defined in the form of lower and upper limits, and a given range is defined by selecting one lower limit and one upper limit, and the selected lower and upper limits define the boundaries of the particular range. Such defined ranges may be inclusive or exclusive of the end values, and any combination is possible; i.e., any lower limit can be combined with any upper limit to form a single range. For example, if ranges of 60 to 120 and 80 to 110 are listed for a particular parameter, it is understood that ranges of 60 to 110 and 80 to 120 are also possible. Furthermore, if 1 and 2 are listed as minimum range values ​​and 3, 4, and 5 are listed as maximum range values, the ranges 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5 are all possible. In this application, unless otherwise specified, a numerical range "a to b" is a shorthand notation for any combination of real numbers a to b, where a and b are both real numbers. For example, the numerical range "0-5" represents that the present specification has already listed all real numbers between "0-5," and "0-5" is merely a shorthand representation of combinations of these numbers. Also, expressing a parameter as an integer ≧2 is equivalent to disclosing that this parameter is, for example, the integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0024] Unless otherwise stated, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0025] Unless otherwise stated, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0026] Unless otherwise stated, all steps in this application may be performed in order or randomly, and in some cases, are performed in order. For example, when a method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed in order, or steps (b) and (a) performed in order. For example, when a method mentioned above may further include step (c), it means that step (c) may be added to the method in any order, and for example, the method may include steps (a), (b), and (c), or may include steps (a), (c), and (b), or may include steps (c), (a), and (b), etc.

[0027] Unless otherwise specified, the terms "comprise" and "include" used in this application may be open-ended or closed-ended. For example, the terms "comprise" and "include" may further include or include other components not listed, or may include or include only the listed components.

[0028] Unless otherwise stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B." More specifically, "A or B" is satisfied when A is true (or exists) and B is false (or does not exist), when A is false (or does not exist) but B is true (or exists), or when both A and B are true (or exist).

[0029] In this application, the definition and test method for fracture toughness are as follows:

[0030] Definition: Fracture toughness is a parameter that describes the ability of a material to absorb strain energy before fracture occurs. Higher fracture toughness represents a stronger ability to inhibit crack propagation. It also reflects the ability of a solid electrolyte membrane to resist dendrite cleavage and short-circuiting. Fracture toughness can be measured using test methods such as four-point bending and Vickers cone indentation. In this application, Vickers cone indentation is selected for measurement.

[0031] Test method: The surface of the solid electrolyte sheet obtained by manufacturing the solid electrolyte membrane is polished with sandpaper in an argon gas atmosphere, from 800 mesh to 2000 mesh, 4000 mesh, and 8000 mesh, until the electrolyte surface exhibits mirror-like properties with no obvious defects. Then, an indentation test is performed on the polished surface using a Vickers cone-type indentation tester. The indentation tester is driven with an appropriate load until radial cracks appear at the four corners of the cone-type indentation. Based on the indentation load P, the radial crack extension length C, Young's modulus E, and microhardness HV, the fracture toughness value K is calculated using the following formula: IC can be calculated.

[0032] JPEG2025542396000002.jpg21161

[0033] In the present application, the definition and test method of the surface resistance of the solid electrolyte membrane are as follows.

[0034] Definition: Surface resistance depends on the ionic conductivity and thickness of the solid electrolyte membrane. It is a comprehensive indicator that measures the properties of the solid electrolyte membrane and the forming process, and is also a direct response to the level of ohmic polarization that the solid electrolyte membrane brings to the battery during actual use. The surface resistance of a solid electrolyte membrane is the product of the resistivity ρ (the reciprocal of the ionic conductivity σ) of the solid electrolyte layer and the thickness d of the solid electrolyte layer, and is also the product of the impedance R in the test and the electrochemically active area A of the solid electrolyte membrane. In practice, it is generally tested using electrochemical AC impedance spectroscopy to calculate the corresponding surface resistance.

[0035] Test Method: Taking lithium-ion solid electrolytes as an example, the manufactured solid electrolyte membrane is punched into 10 mm diameter pieces using a cutter die, and a 100 nm thick layer of nickel is uniformly plated on both sides of the electrolyte by physical vapor deposition. The solid electrolyte membrane is then assembled into a pouch cell, connected to an electrochemical workstation via a current collector, and electrochemical impedance tests are performed on the electrolyte membrane at a bias voltage of 10 millivolts (mV) and within a frequency range of 106 hertz (Hz) to 0.1 Hz. The resistance value R is taken as the Z' coordinate value of the point closest to the Z' axis in the low-frequency band of the electrochemical impedance spectrum curve, from right to left. The surface resistance of the electrolyte membrane can be calculated using the following formula, expressed in units of ohms per square centimeter (Ω cm): 2 ) where A is the area of ​​the solid electrolyte membrane.

[0036] Ω areal =R*A

[0037] Currently, inorganic ceramic solid electrolytes have fragile mechanical properties, making them prone to cracking and dendrites and short circuits when deposited on the negative electrode. Conventional methods involve incorporating fibers into the solid electrolyte to improve the mechanical properties of the solid electrolyte membrane and reduce the occurrence of dendrites and short circuits due to fracture. For example, polymer fast ion conductor fibers are incorporated into the solid electrolyte material. However, these fibers do not exert a sufficiently strong mechanical force, and polymer fast ion conductor fibers have a relatively high overvoltage. Therefore, lithium deposition occurs preferentially within the polymer or at the interface between the polymer and the solid electrolyte, resulting in the formation of dendrites and short circuits in solid-state batteries.

[0038] Based on this, some examples of the present application provide a solid electrolyte membrane, which includes a solid electrolyte material layer and a fiber material layer disposed inside the solid electrolyte material layer, wherein the solid electrolyte material layer includes an inorganic ceramic solid electrolyte material, and the fiber material layer includes ceramic fibers.

[0039] The solid electrolyte membrane has a fiber layer containing ceramic fibers disposed inside the solid electrolyte layer, which provides better fiber toughening and strengthens the mechanical properties, particularly the fracture toughness, of the solid electrolyte membrane, thereby reducing the occurrence of fractures. At the same time, the solid electrolyte membrane has a lower surface resistance and a higher ionic conductivity than a membrane without the fiber layer.

[0040] Furthermore, since ceramic fibers themselves do not have the ability to conduct ions, the phenomenon of fiber deposition induced in conventional methods is reduced, further reducing the problems of dendrites and short circuits.

[0041] In some examples, the ceramic fibers are distributed in a staggered pattern. Due to the limitations of the mechanical properties of inorganic ceramic solid electrolyte materials, it is difficult to form a thin solid electrolyte layer. However, when the ionic conductivity is relatively low, it is necessary to minimize the thickness of the solid electrolyte layer in order to reduce the surface resistance. Based on this, the present application further distributes the ceramic fibers in the fiber material layer in a staggered pattern to form a support structure and provide support for the solid electrolyte material. When the solid electrolyte material is molded, it can form a self-supporting electrolyte membrane by simply filling the fiber material layer. This provides higher mechanical strength, while significantly reducing the thickness of the solid electrolyte membrane, thereby reducing the surface resistance and improving the ionic conductivity of the membrane layer.

[0042] As can be appreciated, the "staggered distribution" may be achieved by bonding the ceramic fibers together, or by other methods such as weaving.

[0043] In some examples, the ceramic fibers form a mesh structure. Furthermore, the mesh structure is woven. This woven structure can provide better support. As can be seen, the mesh structure of the woven structure is parallel to the surface of the solid electrolyte membrane that contacts the electrode plate.

[0044] In some examples, the surface porosity of the fibrous layer is 50% to 90%. By appropriately controlling the surface porosity of the fibrous layer, it is possible to control the surface resistance to a relatively low level, increase the ion conduction capacity, optimize the cycle performance of the all-solid-state battery, and provide a relatively good support function. Specifically, the surface porosity of the fibrous layer may be, but is not limited to, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or a range between any two of the foregoing values. Furthermore, the surface porosity of the fibrous layer may be 65% to 75%.

[0045] In some examples, the ceramic fibers include one or more of silicon carbide fibers, silicon nitride fibers, boron nitride fibers, alumina fibers, and silica fibers. Rational selection of the ceramic type can improve the balance between the different toughening effects due to the different strengths of the fiber materials and the affinity between the fiber material and the solid electrolyte material, thereby reducing the problem of localized non-uniform ion conduction due to the introduction of fibers. Furthermore, the ceramic fibers include one or more of silicon carbide fibers, alumina fibers, and silica fibers.

[0046] In some examples, the aspect ratio of the ceramic fibers is ≧5. Furthermore, the aspect ratio of the ceramic fibers is 5 to 100. While a high aspect ratio can improve the self-supporting ability of the fibrous material layer and increase the upper limit of porosity, a too high aspect ratio can increase the difficulty of manufacturing the ceramic fibers, cause the ceramic fibers to aggregate, and increase the difficulty of fabricating a uniform self-supporting structure. Specifically, the aspect ratio of the ceramic fibers includes, but is not limited to, 5, 10, 15, 20, 25, 30, 50, 70, 100, or a range between any two of the above values.

[0047] In some examples, the inorganic ceramic solid electrolyte material includes a lithium ion solid electrolyte material, a sodium ion solid electrolyte material, or a potassium ion solid electrolyte material. Further, the inorganic ceramic solid electrolyte material includes a sulfide-based solid electrolyte material.

[0048] The lithium ion solid electrolyte may be, but is not limited to, a LISICON type solid electrolyte, a NASICON type lithium ion solid electrolyte, a Garnet type solid electrolyte, a LIPON type solid electrolyte, a Perovskite type solid electrolyte, an Anti-Perovskite type lithium ion solid electrolyte, a Thio-LiSICON type solid electrolyte, a Li 10 GeP2S 12 The present invention relates to a solid electrolyte, a lithium ion solid electrolyte, a (100-e)Li2S·e(F2)·f(G2) type solid electrolyte, an Argyrodite type solid electrolyte, a halide type solid electrolyte, and a hydride type solid electrolyte, wherein in the (100-e)Li2S·e(F2)·f(G2) type solid electrolyte, 20≦e≦30, 0≦f≦50, and F2 is selected from the group consisting of B2S3, Al2S3, In2S3, SiS2, G G2 includes one or more of B2O3, Al2O3, In2O3, SiO2, GeO2, SnO2, P2O5, Sb2O5, Bi2O3, WO2, WO3, MoO2, MoO3, Fe2O3, ZnO, MgO, CuO, CaO, LiN, Li2O, LiF, LiCl, LiBr, and LiI.

[0049] Sodium ion solid electrolytes include NASICON type sodium ion solid electrolytes, Na-β-Alumina type solid electrolytes, Na3PS4 type solid electrolytes, and Na 11 Sn2PS 12 The solid electrolyte may include one or more of a perovskite-type solid electrolyte, a trans-perovskite-type solid electrolyte, and a sodium ion hydride-type solid electrolyte.

[0050] The potassium ion solid electrolyte contains one or more of a β-alumina type potassium ion solid electrolyte, an Anti-Perovskite type potassium ion solid electrolyte, a K2Fe4O7 type solid electrolyte, and a KSi2P3 type solid electrolyte.

[0051] For example, the Garnet type solid electrolyte is Li 7-a La3Zr 2-a (A2) a O 12 and here, 0 ≦ a < 1, and A2 contains one or more of Sb, Nb, Ta, Te, and W.

[0052] The Thio-LiSICON type solid electrolyte is Li 3+b (B2) c (C2) 1-c (D2) 4-d (E2) d and here, -1 < b < 2, 0 ≦ c ≦ 1, 0 ≦ d ≦ 2, B2 contains one or more of B, Al, In, Si, Ge, Sn, Ti, W, and Mo, C2 contains one or more of P, As, Sb, and Bi, D2 contains one or more of S and Se, and E2 contains one or more of F, Cl, Br, and I.

[0053] The Argyrodite type solid electrolyte is Li 6+g (H2) h (I2) 1-h (J2) 5-i (K2) 1+i and here, -1 ≦ g ≦ 1, 0 ≦ h ≦ 1, -1 < i ≦ 1, H2 contains one or more of B, Al, In, Si, Ge, Sn, Ti, W, and Mo, I2 contains one or more of P, As, Sb, and Bi, J2 represents one or more of S and Se, and K2 contains one or more of F, Cl, Br, and I.

[0054] The LISICON type solid electrolyte contains γ-Li3PO4.

[0055] The NASICON type lithium ion solid electrolyte is Li 1+j(L2) j (M2) 2-j Contains (PO4)3, where 0 ≦ j < 1, L2 contains one or more of Al, Cr, Ba, Fe, Sc, In, Lu, Y, and La, and M2 contains one or more of Ti and Ge.

[0056] The perovskite-type solid electrolyte is Li 3k (N2) 2 / 3-k Contains (Q2)O3, where 0.04 < k < 0.17, N2 contains one or more of La, Sr, Ba, and Nd, and Q2 contains one or more of Al, Ti, and Ge.

[0057] The anti-perovskite-type lithium ion solid electrolyte contains Li3OCl.

[0058] Li 10 GeP2S 12 The type solid electrolyte is Li 10+l (R2) 1+m (S2) 2-m (T2) 12-n (U2) n Contains, where -2 < l < 2, 0 ≦ m ≦ 2, 0 ≦ n ≦ 2, R2 contains one or more of B, Al, In, Si, Ge, Sn, Ti, W, and Mo, S2 contains one or more of P, As, Sb, and Bi, T2 contains one or more of S and Se, and U2 contains one or more of F, Cl, Br, and I.

[0059] The halide-type solid electrolyte contains one or more of Li3(V2)(W2)6 and Li2Sc 2 / 3 (W2)4, where V2 contains one or more of Y, Er, In, Sc, and Ga, and W2 contains one or more of F, Cl, Br, and I.

[0060] The hydride-type lithium ion solid electrolyte is LiBH4 and pLi(CB9H 10 )·(1 - p)Li(CB 11 H 12including one or more of them, where 0 < p < 1.

[0061] The LIPON-type solid electrolyte contains Li x PO y N z etc., where (2y + 3z - x = 5, x ≥ 1, y ≥ 1, z ≥ 0).

[0062] The NASICON-type sodium ion solid electrolyte contains Na 1+t+2u Zr 2-u (A3) u P 3-t Si t O 12 and here, 0 ≤ t ≤ 3, 0 ≤ u ≤ 1, and A3 contains one or more of Zn, Mg, and Ca.

[0063] The Na-β-Alumina-type solid electrolyte contains one or more of Na2O·(5 - 7)Al2O3 and Na2O·(8 - 11)Al2O3.

[0064] The Na3PS4-type solid electrolyte contains Na 3+x (B3) v (C3) 1-v (D3) 4-w (E3) w and here, -1 < x < 2, 0 ≤ v ≤ 1, 0 ≤ w ≤ 2, B3 contains one or more of B, Al, In, Si, Ge, Sn, Ti, W, and Mo, C3 contains one or more of P, As, Sb, and Bi, D3 contains one or more of S and Se, and E3 represents one or more of F, Cl, Br, and I.

[0065] Na 11 Sn2PS 12 type solid electrolyte contains Na <l 11+(x1) (F3) 2-y (G3) 1+y (H3) 12-z (J3) zincluding, where -1 < x1 < 1, 0 ≤ y ≤ 2, 0 ≤ z ≤ 2, F3 contains one or more of B, Al, In, Si, Ge, Sn, Ti, W and Mo, G3 contains one or more of P, As, Sb and Bi, H3 contains one or more of S and Se, and J3 contains one or more of F, Cl, Br and I.

[0066] The perovskite-type solid electrolyte contains Na3O(K3), where K3 contains one or more of Cl, Br, I and BH4.

[0067] The Hydride-type sodium ion solid electrolyte contains Na2C (b1) B (a1)-(b1) H (b1) and Na(BH4) 0.5 (NH2) 0.5 etc., where a1 = 10 or 12 and b1 = 0 or 1.

[0068] The β-Alumina-type potassium ion solid electrolyte contains K2O·(8 - 11)Al2O3.

[0069] The Anti-Perovskite-type potassium ion solid electrolyte contains K3OI.

[0070] The K2Fe4O7-type solid electrolyte contains K2Fe4O7.

[0071] The KSi2P3-type solid electrolyte contains KSi2P3.

[0072] Furthermore, by the above film layer design, the fracture toughness of the solid electrolyte membrane can be effectively improved. In some of these examples, the fracture toughness of the solid electrolyte membrane is ≥ 0.25 megapascals per square root of a meter (MPa·m 1 / 2 ). Furthermore, the fracture toughness of the solid electrolyte membrane is ≥ 0.3 MPa·m 1 / 2 . Specifically, the fracture toughness of the solid electrolyte membrane is 0.27 MPa·m 1 / 2 , 0.32 MPa·m 1 / 2 , 0.33 MPa·m1 / 2 , 0.34 MPa·m 1 / 2 , 0.36 MPa·m 1 / 2 , 0.41 MPa·m 1 / 2 , 0.43 MPa·m 1 / 2 , 0.49 MPa·m 1 / 2 , 0.67 MPa·m 1 / 2 , 0.87 MPa·m 1 / 2 At the same time, it can be understood that the fracture toughness is related to the type of solid electrolyte material. In some examples of the present application, for example, when the inorganic ceramic solid electrolyte material includes a sulfide-based solid electrolyte material, the above performance can be met, and when the solid electrolyte material is another type of material, the fracture toughness can be 0.25 MPa m 1 / 2 For example, in some instances, the fracture toughness of the solid electrolyte membrane may be ≥ 0.05 MPa m 1 / 2 On the other hand, when the solid electrolyte material used is the same, the fracture toughness of the solid electrolyte membrane can be improved by adopting the solution of the above example of the present application.

[0073] The above membrane layer design allows the thickness of the solid electrolyte membrane to be reduced, for example, to 200% or less of the thickness of the fiber material layer, and further reduces the surface resistance. In some examples, the surface resistance of the solid electrolyte membrane is ≦5 Ω cm. 2 Furthermore, the surface resistance of the solid electrolyte membrane is ≦2 Ω cm 2 Specifically, the surface resistance of the solid electrolyte membrane is 0.73 Ω cm 2 , 0.76 Ω·cm 2 , 0.78 Ω·cm 2 , 0.87 Ω·cm 2 , 0.93 Ω·cm 2 , 1.07 Ω·cm 2 , 1.13 Ω·cm 2 , 1.21 Ω·cm 2 , 1.37 Ω·cm 2 , 2.34 Ω·cm 2 , 4.83 Ω·cm 2At the same time, it can be understood that the surface resistance is related to the type of solid electrolyte material. In some examples of the present application, for example, when the inorganic ceramic solid electrolyte material includes a sulfide-based solid electrolyte material, the above performance can be met, and when the solid electrolyte material is another type of material, the surface resistance is 5 Ω cm or less. 2 For example, in some cases, the surface resistance of the solid electrolyte membrane is ≦50 Ω cm 2 On the other hand, when the solid electrolyte material used is the same, the surface resistance of the solid electrolyte membrane can be reduced by adopting the solution of the above example of the present application.

[0074] In some embodiments, the thickness of the solid electrolyte membrane is ≦80 microns (μm). Further, the thickness of the solid electrolyte membrane is ≦60 μm. Specifically, the thickness of the solid electrolyte membrane includes, but is not limited to, 40 μm, 45 μm, 50 μm, 60 μm, and 80 μm.

[0075] Some other examples of the present application provide a method for producing the above-described solid electrolyte membrane, the method for producing the solid electrolyte membrane comprising: employing ceramic fibers to fabricate the fiber material layer; and coating the inorganic ceramic solid electrolyte material on the surface of the fiber material layer and filling gaps in the fiber material layer with the inorganic ceramic solid electrolyte material, and then forming the inorganic ceramic solid electrolyte material to produce the solid electrolyte membrane.

[0076] The above-mentioned solid electrolyte membrane manufacturing method uses a fiber material layer directly as a substrate, and then coats and fills the fiber material layer to form a solid electrolyte membrane with an internal support structure in situ, improving the mechanical properties of the solid electrolyte membrane, and eliminating the need to physically mix the solid electrolyte and the fiber material in advance, thereby simplifying the operation steps.

[0077] In some of these examples, the step of producing the textile layer comprises: The ceramic fibers are distributed in a staggered pattern to form the fibrous material layer.

[0078] While having such higher mechanical strength, the thickness of the solid electrolyte membrane can be significantly reduced, reducing the surface resistance and improving the ionic conductivity of the membrane layer. As can be understood, the "staggered distribution" can be achieved by bonding the ceramic fibers together or by knitting or other methods.

[0079] In some examples, the ceramic fibers form a mesh structure. Furthermore, the mesh structure is woven. This woven structure can provide better support. As can be seen, the mesh structure of the woven structure is parallel to the surface of the solid electrolyte membrane that contacts the electrode plate.

[0080] In some of these examples, the step of fabricating the solid electrolyte membrane includes: mixing the inorganic ceramic solid electrolyte material, an adhesive and a solvent to prepare an electrolyte slurry, or preparing an electrolyte powder from the inorganic ceramic solid electrolyte material; and coating and filling the electrolyte slurry or powder.

[0081] As can be seen, the inorganic ceramic solid electrolyte material is generally in powder form and has a certain fluidity. On the one hand, a fiber material layer can be directly injected to coat and fill the layer, or an adhesive can be added during the electrolyte powder preparation process, if necessary. On the other hand, the inorganic ceramic solid electrolyte material can be mixed with a solvent to form a slurry, and then a fiber material layer can be injected to coat and fill the layer. The type of solvent is not particularly limited, and examples include one or more of toluene, p-xylene, o-xylene, m-xylene, mesitylene, ethyl acetate, butyl butyrate, n-butyl ether, anisole, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and n-butane. The amount used can be reasonably controlled according to the fluidity of the slurry.

[0082] In some examples, the adhesive may include one or more of nitrile rubber (NBR), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyimide (PI), polyacrylonitrile (PAN), polyurethane (PU), polycarboxymethylcellulose (CMC), cyclodextrin (CD), sodium alginate (SA), polysaccharide, and styrene butadiene rubber (SBR), and the amount used may be reasonably controlled according to the formation of the solid electrolyte membrane.

[0083] In some examples, the forming step includes one or both of drying and pressing. As can be understood, in the process of producing the solid electrolyte membrane by the method of producing an electrolyte slurry, the solvent must be removed by drying and then the membrane layer must be densified by pressing. In the process of producing the solid electrolyte membrane by the method of producing an electrolyte powder, the membrane layer may be densified by directly pressing.

[0084] Furthermore, the pressure of the pressurization treatment is 10 megapascals (MPa) to 600 MPa.

[0085] The solid-state battery, battery module, battery pack, and power consuming device of the present application will be described below with appropriate reference to the drawings.

[0086] One embodiment of the present application provides a solid-state battery.

[0087] Generally, a solid-state battery includes a positive electrode plate, a negative electrode plate, and an electrolyte. During charging and discharging of the battery, active ions are repeatedly absorbed and released between the positive electrode plate and the negative electrode plate. The electrolyte serves to conduct ions between the positive electrode plate and the negative electrode plate. Specifically, the electrolyte is the solid electrolyte layer described above.

[0088] The positive electrode plate includes a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector, and the positive electrode active material layer includes the positive electrode active material of the first aspect of the present application.

[0089] For example, the positive electrode current collector has two surfaces facing each other in the thickness direction thereof, and the positive electrode active material layer is disposed on either one or both of the two facing surfaces of the positive electrode current collector.

[0090] In some embodiments, the positive electrode current collector may be a metal foil sheet or a composite current collector. For example, aluminum foil may be used as the metal foil sheet. The composite current collector may include a polymer base layer and a metal layer formed on at least one surface of the polymer base layer. The composite current collector may be formed by forming a metal material (such as aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver, or silver alloy) on a polymer substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), or polyethylene (PE)).

[0091] In some embodiments, the positive electrode active material may be a positive electrode active material for batteries known in the art. For example, the positive electrode active material may include at least one of a lithium-containing phosphate with an olivine structure, a lithium transition metal oxide, and a modified compound thereof. However, the present application is not limited to these materials, and other conventional materials usable 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. Here, examples of lithium transition metal oxides include lithium cobalt oxide (e.g., LiCoO), lithium nickel oxide (e.g., LiNiO), lithium manganese oxide (e.g., LiMnO, LiMnO), lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, and lithium nickel cobalt manganese oxide (e.g., LiNi). 1 / 3 Co 1 / 3 Mn 1 / 3 O2(NCM 333 (may be abbreviated as "LiNi") 0.5 Co 0.2 Mn 0.3 O2(NCM 523 (may be abbreviated as "LiNi") 0.5 Co 0.25 Mn 0.25 O2(NCM 211 (may be abbreviated as "LiNi") 0.6 Co 0.2 Mn 0.2 O2(NCM 622 (may be abbreviated as "LiNi") 0.8 Co 0.1 Mn 0.1 O2(NCM 811 ), lithium nickel cobalt aluminum oxide (e.g., LiNi 0.8 Co 0.15 Al 0.05Examples of the lithium-containing phosphate having an olivine structure may include, but are not limited to, at least one of lithium iron phosphate (e.g., LiFePO4 (which may be abbreviated as LFP)), a composite material of lithium iron phosphate and carbon, lithium manganese phosphate (e.g., LiMnPO4), a composite material of lithium manganese phosphate and carbon, lithium manganese iron phosphate, and a composite material of lithium manganese iron phosphate and carbon.

[0092] In some embodiments, the positive electrode active material layer may further include an adhesive, for example, at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and a fluorine-containing acrylate resin.

[0093] In some embodiments, the positive electrode active material layer may further include a conductive agent, for example, superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.

[0094] In some embodiments, the positive electrode plate can be manufactured in the following manner: The components for manufacturing the positive electrode plate, such as the positive electrode active material, conductive agent, adhesive, and any other components, are dispersed in a solvent (e.g., N-methylpyrrolidone) to form a positive electrode slurry, which is then coated on a positive electrode current collector, and the positive electrode plate is obtained after processes such as drying and cold pressing.

[0095] The negative electrode plate includes a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector, and the negative electrode active material layer includes a negative electrode active material.

[0096] For example, the negative electrode current collector has two surfaces facing each other in the thickness direction thereof, and the negative electrode active material layer is disposed on either one or both of the two facing surfaces of the negative electrode current collector.

[0097] In some embodiments, the negative electrode current collector may be a metal foil sheet or a composite current collector. For example, the metal foil sheet may be copper foil. The composite current collector may include a polymer base layer and a metal layer formed on at least one surface of the polymer base. The composite current collector may be formed by forming a metal material (such as copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver, or silver alloy) on a polymer base (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), or polyethylene (PE)).

[0098] In some embodiments, the negative electrode active material may be a battery negative electrode active material known in the art. For example, the negative electrode active material may include at least one of lithium metal, lithium-containing alloy, lithium-containing composite, artificial graphite, natural graphite, soft carbon, hard carbon, silicone-based material, tin-based material, and lithium titanate. The silicone-based material may be selected from at least one of silicone, silicone oxide, silicone carbon composite, silicone nitrogen composite, and silicone alloy. The tin-based material may be selected from at least one of tin, tin oxide, and tin alloy. However, the present application is not limited to these materials and may also use other conventional materials that can be used as battery negative electrode active materials. These negative electrode active materials may be used alone or in combination.

[0099] In some embodiments thereof, the negative electrode active material layer optionally further includes an adhesive, which may be selected from at least one of styrene butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).

[0100] In some embodiments, the negative electrode active material layer may further include a conductive agent, which may be selected from the group consisting of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.

[0101] In some of the embodiments, the negative electrode active material layer further optionally contains other additives, such as a thickener (eg, carboxymethylcellulose sodium (CMC-Na)).

[0102] In some embodiments, the negative electrode plate can be manufactured in the following manner: Components for manufacturing the negative electrode plate, such as a negative electrode active material, a conductive agent, an adhesive, and any other components, are dispersed in a solvent (e.g., deionized water) to form a negative electrode slurry, which is then coated on a negative electrode current collector, and the negative electrode plate is obtained after processes such as drying and cold pressing.

[0103] The present application does not particularly limit the shape of the solid-state battery, which may be cylindrical, rectangular, or any other shape. For example, FIG. 1 shows an example of a rectangular solid-state battery 5.

[0104] In some embodiments, the solid-state batteries may be assembled into a battery module, and the number of solid-state batteries included in the battery module may be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery module.

[0105] Fig. 2 shows an example of a battery module 4. Referring to Fig. 2, in the battery module 4, a plurality of solid-state batteries 5 may be arranged in order along the longitudinal direction of the battery module 4. Of course, they may be arranged in any other manner. Furthermore, the plurality of solid-state batteries 5 may be fixed by fasteners.

[0106] Optionally, the battery module 4 may further include a housing having an accommodating space, and the plurality of solid-state batteries 5 are accommodated in the accommodating space.

[0107] In some embodiments, the battery modules may be further assembled into a battery pack, and the number of battery modules included in the battery pack may be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery pack.

[0108] 3 and 4 show an example of a battery pack 1. Referring to FIGS. 3 and 4, the battery pack 1 may include a battery box and a plurality of battery modules 4 installed in the battery box. The battery box includes an upper housing 2 and a lower housing 3, and the upper housing 2 covers the lower housing 3 to form a sealed space for accommodating the battery modules 4. The plurality of battery modules 4 may be arranged in the battery box in any manner.

[0109] The present application also provides a power consuming device, the power consuming device including at least one of the solid-state battery, battery module, or battery pack according to the present application. The solid-state battery, battery module, or battery pack may be used as a power source for the power consuming device or as an energy storage unit for the power consuming device. The power consuming device may include, but is not limited to, a mobile device, an electric vehicle, an electric train, a ship, a satellite, an energy storage system, etc. Here, the mobile device may be, for example, a mobile phone, a laptop, etc., and the electric vehicle may be, for example, a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc., but is not limited to these.

[0110] As the power consuming device, a solid-state battery, a battery module, or a battery pack can be selected according to the usage demand.

[0111] 5 shows an example power consuming device 6, which may be a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle. To meet the demand for high power and high energy density of solid-state batteries in this power consuming device, a battery pack or battery module may be employed.

[0112] Another example of the device may be a mobile phone, a tablet computer, a laptop computer, etc. These devices are generally required to be thin and may employ a solid-state battery as a power source.

[0113] The following describes examples of the present application. The examples described below are illustrative and are intended to interpret the present application, but should not be understood as limitations on the present application. If no specific techniques or conditions are described in the examples, they are carried out according to the techniques, conditions, or product specifications described in documents within the field. If no manufacturer is specified for the reagents or equipment used, they are all ordinary products that are commercially available.

[0114] Example 1 (1) Li6PS5Cl solid electrolyte powder, NBR adhesive, and p-xylene were mixed in a mass ratio of 44.1:0.9:55, and mixed in a planetary ball mill at a speed of 200 rpm for 2 hours to ensure thorough mixing, producing a slurry; (2) Al2O3 fibers (aspect ratio 20) are woven into a substrate layer with a thickness of 30 μm and a surface porosity of 50%, the structure of which is shown in Figure 6 (Figure 6 shows the substrate layer exposed after peeling off the solid electrolyte material on the surface of the produced solid electrolyte membrane). After the Al2O3 substrate layer is fixed, the slurry produced in step (1) is applied in a dry environment using a 75 μm scraper on a flat coater. During application, the slurry quickly enters the gaps in the substrate layer based on the fluidity of the slurry, filling and covering the substrate layer so that the substrate layer is not exposed. (3) The electrolyte membrane after coating in step (2) was dried in a vacuum environment and then compressed using a flat press to a pressure of 500 MPa to form a solid electrolyte membrane with a thickness of 50 μm.

[0115] Examples 2 to 11 and Comparative Example 1 are based on Example 1, but the surface porosity of the substrate layer, the type of fiber, and the type of solid electrolyte material are changed, and the remaining steps are the same as those of Example 1, as shown in Table 1.

[0116] In Comparative Example 2, the substrate layer was not prepared according to Example 1, but the slurry of step (1) was directly coated on a PET film, dried, and compressed to form a self-supporting solid electrolyte membrane.

[0117] The solid electrolytes produced in the examples and comparative examples were subjected to surface resistance and fracture toughness tests, and the results are shown in Table 1.

[0118] [Table 1]

[0119] It should be noted that the present application is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any embodiment that has substantially the same configuration as the technical idea and achieves the same effects within the scope of the technical solution of the present application is included within the technical scope of the present application. In addition, various modifications that a person skilled in the art can make to the embodiments and other methods that are configured by combining some of the components of the embodiments are also included within the scope of the present application, as long as they do not deviate from the spirit of the present application. [Explanation of symbols]

[0120] 1: Battery pack, 2: Upper housing, 3: Lower housing, 4: Battery module, 5: Solid-state battery, 6: Power consumption device.

Claims

1. 1. A solid electrolyte membrane comprising: a solid electrolyte material layer; and a fiber material layer disposed inside the solid electrolyte material layer, wherein the solid electrolyte material layer contains an inorganic ceramic solid electrolyte material; the fiber material layer contains ceramic fibers; the ceramic fibers form a mesh structure; and the mesh structure is formed by knitting.

2. The solid electrolyte membrane according to claim 1 , wherein the mesh structure is parallel to a surface of the solid electrolyte membrane that is to contact an electrode plate.

3. 3. The solid electrolyte membrane according to claim 1, wherein the surface porosity of the fiber material layer is 50% to 90%.

4. 4. The solid electrolyte membrane according to claim 3, wherein the surface porosity of the fiber material layer is 65% to 75%.

5. 5. The solid electrolyte membrane according to claim 1, wherein the ceramic fibers include one or more of silicon carbide fibers, silicon nitride fibers, boron nitride fibers, alumina fibers, and silica fibers.

6. 6. The solid electrolyte membrane according to claim 1, wherein the aspect ratio of the ceramic fibers is ≧5.

7. 7. The solid electrolyte membrane according to claim 6, wherein the aspect ratio of the ceramic fibers is 5 to 100.

8. The solid electrolyte membrane according to any one of claims 1 to 7, wherein the inorganic ceramic solid electrolyte material comprises a lithium ion solid electrolyte material, a sodium ion solid electrolyte material, or a potassium ion solid electrolyte material.

9. The solid electrolyte membrane has one or more of the following characteristics (1) to (3): (1) The fracture toughness of the solid electrolyte membrane is ≧0.25 MPa m １／２ and (2) The surface resistance of the solid electrolyte membrane is ≦5 Ω·cm ２ and (3) The solid electrolyte membrane according to any one of claims 1 to 8, wherein the thickness of the solid electrolyte membrane is ≦80 μm.

10. The solid electrolyte membrane has one or more of the following characteristics (1) to (3): (1) The fracture toughness of the solid electrolyte membrane is ≧0.3 MPa m １／２ and (2) The surface resistance of the solid electrolyte membrane is ≦2 Ω·cm ２ and (3) The solid electrolyte membrane according to claim 9, wherein the thickness of the solid electrolyte membrane is ≦60 μm.

11. A method for producing a solid electrolyte membrane according to any one of claims 1 to 10, A step of manufacturing the fiber material layer by using ceramic fibers, the ceramic fibers forming a mesh structure, and the mesh structure adopting a knitting method; and coating the inorganic ceramic solid electrolyte material on the surface of the fiber material layer and filling gaps in the fiber material layer with the inorganic ceramic solid electrolyte material, and then performing a molding process to produce the solid electrolyte membrane.

12. The step of manufacturing the solid electrolyte membrane includes: mixing the inorganic ceramic solid electrolyte material, an adhesive and a solvent to prepare an electrolyte slurry, or preparing an electrolyte powder from the inorganic ceramic solid electrolyte material; The method for producing a solid electrolyte membrane according to claim 11, further comprising the step of coating and filling with the electrolyte slurry or electrolyte powder.

13. 13. The method for producing a solid electrolyte membrane according to claim 12, wherein the adhesive comprises one or more of nitrile rubber, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, polyvinyl alcohol, polyimide, polyacrylonitrile, polyurethane, polycarboxymethyl cellulose, cyclodextrin, sodium alginate, polysaccharides, and styrene butadiene rubber.

14. The method for producing a solid electrolyte membrane according to any one of claims 11 to 13, wherein the forming step includes one or both of drying and pressure treatment.

15. The method for producing a solid electrolyte membrane according to claim 14, wherein the pressure of the pressurization treatment is 10 MPa to 600 MPa.

16. A solid-state battery comprising the solid electrolyte membrane according to any one of claims 1 to 10.

17. 17. A power consuming device comprising the solid state battery of claim 16.

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