Positive electrode sheet, solid-state battery cell, battery apparatus, electrical apparatus, halide solid-state electrolyte material and preparation method therefor

Abstract

Provided in the present disclosure are a positive electrode sheet, a solid-state battery cell, a battery apparatus, an electrical apparatus, a halide solid-state electrolyte material and a preparation method therefor. The positive electrode sheet comprises a positive electrode active material and a halide solid-state electrolyte material, the halide solid-state electrolyte material being in an amorphous state. The molecular formula of the halide solid-state electrolyte material is LiM1 xM2 yX6, M1 comprising one or two elements of Ta and Nb, M2 comprising one or more of trivalent metal elements and tetravalent metal elements, X comprising one or more of halogen elements, 0.5≤x＜1, and LiM1 xM2 yX6 being electrically neutral. The positive electrode sheet is applied to a solid-state battery cell, and can improve the cycling stability and rate performance of the solid-state battery cell.

Description

Cathode sheet, solid-state battery monomer, battery device, power utilization device, halide solid-state electrolyte material and preparation method thereof

[0001] Cross-reference to Related Applications

[0002] This application claims priority to Chinese Patent Application No. 202411237764.2, filed on September 4, 2024, entitled “Cathode sheet, solid-state battery monomer, battery device, power utilization device, halide solid-state electrolyte material and preparation method thereof”, the entire contents of which are incorporated herein by reference. TECHNICAL FIELD

[0003] The present disclosure relates to a cathode sheet, a solid-state battery monomer, a battery device, a power utilization device, a halide solid-state electrolyte material and a preparation method thereof. BACKGROUND

[0004] Compared with liquid battery monomers, solid-state battery monomers use solid-state electrolyte materials, and are less likely to catch fire or explode, thereby having high energy density and high reliability. However, the contact between the electrodes and the electrolyte sheet of the solid-state battery monomer is solid-solid contact, the ion transmission channel is less, and the ion transmission is more difficult, thereby affecting the electrochemical performance of the solid-state battery monomer. SUMMARY

[0005] The present disclosure provides a cathode sheet, a solid-state battery monomer, a battery device, a power utilization device, a halide solid-state electrolyte material and a preparation method thereof, the cathode sheet is applied to the solid-state battery monomer, and can improve the cycle stability and rate performance of the solid-state battery monomer.

[0006] In a first aspect, the present disclosure provides a cathode sheet, the cathode sheet comprising a positive electrode active material and a halide solid-state electrolyte material, the halide solid-state electrolyte material being amorphous, the molecular formula of the halide solid-state electrolyte material being LiM 1 x M 2 y X6, M 1 comprising one or both of Ta and Nb, M 2 comprising one or more of a trivalent metal element and a tetravalent metal element, X comprising one or more of a halogen element, 0.5≤x<1, and LiM 1 x M 2 y X6is electrically neutral.

[0007] The present disclosure improves the cycle stability and rate performance of the solid-state battery monomer by using the halide solid-state electrolyte material as the cathode sheet of the solid-state battery monomer. 1The Ta site and / or the Nb site of X6 is doped with one or more of a trivalent metal element and a tetravalent metal element, and the halide solid-state electrolyte material is in an amorphous state, the microstructure of the halide solid-state electrolyte material can be adjusted, the ionic conductivity and stability of the halide solid-state electrolyte material are improved, especially the stability of the halide solid-state electrolyte material relative to the sulfide solid-state electrolyte material, so that the solid-state battery monomer has higher ion transmission characteristics. The positive electrode sheet of the present disclosure is applied to the solid-state battery monomer, which can improve the cycle stability and rate performance of the solid-state battery monomer.

[0008] In some embodiments, the halide solid-state electrolyte material is coated on at least part of the surface of the positive electrode active material. In this way, the crystal structure of the positive electrode active material can be stabilized, and the ion transmission characteristics of the solid-state battery monomer are further improved, and the cycle stability and rate performance of the solid-state battery monomer are improved.

[0009] In some embodiments, 0.6≤x≤0.9. In this way, the ionic conductivity of the halide solid-state electrolyte material can be further improved, and the cycle stability and rate performance of the solid-state battery monomer can also be improved.

[0010] In some embodiments, M 1 Includes Ta. In this way, the solid-state battery monomer has higher ion transmission characteristics, good cycle stability, and good rate performance.

[0011] In some embodiments, M 2 Includes one or more elements of Bi, Sb, As, Sc, Y, La, Pr, Nd, Eu, Gd, Tb, Ho, Er, Tm, Yb, Lu, Zr, Hf, Ce, and Ge.

[0012] Optionally, M 2 Includes one or more elements of Y, Zr, and Hf.

[0013] In some embodiments, X includes one or more elements of Cl, Br, and F.

[0014] In some embodiments, X includes Cl, or X includes Cl and F, or X includes Cl and Br, or X includes Cl, Br, and F.

[0015] In some embodiments, the molecular formula of the halide solid-state electrolyte material is LiM 1 x M 2 y Cl 6-z F z , 0.1≤z≤0.5.

[0016] In some embodiments, the molecular formula of the halide solid-state electrolyte material is LiM1 x M 2 y Cl 6-p-z Br p F z 0.1≤p≤3, 0.1≤z≤0.5.

[0017] In some embodiments, the mass ratio of the positive electrode active material to the halide solid electrolyte material is 99:1 to 60:40. Thereby, the solid-state battery cell can have high energy density and high ion transport properties.

[0018] In some embodiments, the halide solid electrolyte material has a volume distribution particle size Dv90 of 0.5 μm-3 μm.

[0019] In some embodiments, the positive electrode active material has a volume distribution particle size Dv50 of 3 μm-5 μm.

[0020] In some embodiments, the halide solid electrolyte material has an ionic conductivity of 2 mS / cm-7 mS / cm at 25°C.

[0021] In some embodiments, the positive electrode active material includes one or more of lithium transition metal oxides and modified materials thereof, lithium-containing phosphates and modified materials thereof, lithium titanate, sulfur, selenium, tellurium.

[0022] In some embodiments, the positive electrode sheet further includes a positive electrode conductive agent and / or a positive electrode binder.

[0023] In some embodiments, the positive electrode sheet further includes a positive electrode current collector, and the positive electrode active material and the solid electrolyte material are located on at least one surface of the positive electrode current collector.

[0024] In a second aspect, the disclosure provides a solid-state battery cell including a negative electrode sheet, an electrolyte sheet, and the positive electrode sheet of the first aspect, the electrolyte sheet being located between the negative electrode sheet and the positive electrode sheet.

[0025] In some embodiments, the negative electrode sheet includes one or more of graphite, graphene, carbon nanotubes, mesophase carbon microbeads, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, metal oxides, lithium, lithium alloys, lithium composite materials.

[0026] In some embodiments, the electrolyte sheet includes a sulfide solid electrolyte material.

[0027] In a third aspect, the disclosure provides a battery device including a plurality of the solid-state battery cells of the second aspect.

[0028] In a fourth aspect, the disclosure provides an electrically powered device including the solid-state battery cell of the third aspect or the battery device of the fourth aspect.

[0029] In a fifth aspect, the present disclosure provides a halide solid-state electrolyte material, the halide solid-state electrolyte material being in an amorphous state, and a molecular formula of the halide solid-state electrolyte material being LiM 1 x M 2 y X6, M 1 comprising one or both of Ta and Nb, M 2 comprising one or more of a trivalent metal element and a tetravalent metal element, X comprising one or more of a halogen element, 0.5≤x<1, and LiM 1 x M 2 y X6is electrically neutral.

[0030] In a sixth aspect, the present disclosure provides a method for preparing a halide solid-state electrolyte material, comprising the following steps: in an inert atmosphere, ball-milling a halide of M 1 , a halide of M 2 , and a halide of Li in a stoichiometric ratio, to obtain an amorphous LiM 1 x M 2 y X6, M 1 comprising one or both of Ta and Nb, M 2 comprising one or more of a trivalent metal element and a tetravalent metal element, X comprising one or more of a halogen element, 0.5≤x<1, and LiM 1 x M 2 y X6is electrically neutral. BRIEF DESCRIPTION OF DRAWINGS

[0031] In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the following will briefly introduce the drawings needed to be used in the embodiments of the present disclosure. Obviously, the drawings described below are only some of the embodiments of the present disclosure, and other drawings can also be obtained according to the drawings without creative labor.

[0032] FIG. 1 shows an X-ray diffraction pattern (XRD) of a halide solid-state electrolyte material prepared in Example 1.

[0033] FIG. 2 shows an X-ray diffraction pattern (XRD) of a halide solid-state electrolyte material prepared in Comparative Example 2.

[0034] In the drawings, the drawings are not necessarily drawn according to the actual proportions. DETAILED DESCRIPTION

[0035] Hereinafter, specific embodiments of the positive electrode sheet, the solid-state battery cell, the battery device, the power consuming device, the halide solid electrolyte material, and the method for producing the same according to the present disclosure will be described in detail with appropriate reference to the accompanying drawings. However, there will be cases where unnecessary detailed description is omitted. For example, there will be cases where detailed description of matters known well, redundant description of substantially identical structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided to enable those skilled in the art to fully understand the present disclosure, and are not intended to limit the subject matter recited in the claims.

[0036] The ranges disclosed by the present disclosure 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 limit and upper limit define the boundaries of a particular range. The ranges defined in this way can be inclusive or exclusive of the end values, and can be arbitrarily combined, i.e., any lower limit can be combined with any upper limit to form a range. For example, if the ranges 60-120 and 80-110 are listed for a particular parameter, it is understood that the ranges 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In the present disclosure, unless otherwise stated, a numerical range "a-b" represents a shorthand manner of describing the arbitrary real number combinations between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed herein, and "0-5" is just a shorthand notation for these numerical combinations. In addition, when it is stated that a certain parameter is an integer ≥ 2, it is equivalent to disclose that the parameter is, for example, an integer 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and the like.

[0037] Unless otherwise specified, all embodiments and optional embodiments of the present disclosure can be combined with each other to form new technical solutions, and such technical solutions should be considered to be included in the disclosure of the present disclosure.

[0038] Unless otherwise specified, all technical features and optional technical features of the present disclosure can be combined with each other to form new technical solutions, and such technical solutions should be considered to be included in the disclosure of the present disclosure.

[0039] If not otherwise specified, all steps of the present disclosure can be performed in sequence or randomly, preferably in sequence. For example, the method comprising steps (a) and (b) means that the method can comprise steps (a) and (b) in sequence, or steps (b) and (a) in sequence. For example, the method comprising step (c) means that step (c) can be added to the method in any sequence, for example, the method can comprise steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0040] If not otherwise specified, in the present disclosure, the terms "first", "second", etc. are used to distinguish different objects, rather than to describe a specific sequence or primary and secondary relationship.

[0041] In the present disclosure, the terms "a plurality of" and "a plurality of kinds" mean two or more.

[0042] In the description of the embodiments of the present disclosure, if not otherwise specified, the first feature is "on" or "under" the second feature can mean that the first and second features are in direct contact, or the first and second features are in indirect contact through an intermediate medium. Moreover, the first feature can be "above", "over" and "on" the second feature, which can mean that the first feature is directly above or obliquely above the second feature, or only means that the first feature is horizontally higher than the second feature. The first feature can be "under", "below" and "underneath" the second feature, which can mean that the first feature is directly below or obliquely below the second feature, or only means that the first feature is horizontally lower than the second feature.

[0043] Unless otherwise specified, the test temperature of each parameter mentioned in the present disclosure is 25℃.

[0044] The solid-state battery cell mentioned in the embodiments of the present disclosure can realize the function of charging and discharging independently, and can continue to be used by activating the active material through charging after discharging.

[0045] The battery apparatus mentioned in the embodiments of the present disclosure can comprise one or more battery cell assemblies for providing voltage and capacity. The battery cell assembly can comprise a plurality of solid-state battery cells connected in series, in parallel or in mixed connection through a busbar component.

[0046] In some embodiments, the battery cell assembly is usually formed by arranging a plurality of solid-state battery cells.

[0047] As an example, the battery cell assembly can be a battery module, which is formed by arranging and fixing a plurality of solid-state battery cells into one independent module. As an example, the battery module can be formed by bundling a plurality of solid-state battery cells by a cable tie.

[0048] In some embodiments, the battery device can be a battery pack, which includes a case and one or more battery cell assemblies, the battery cell assemblies being accommodated in the case.

[0049] As an example, the battery cell assembly can be a battery module, which can be accommodated in the case by fixing the battery module in the case.

[0050] As an example, the battery cell assembly can also be accommodated in the case by directly fixing a plurality of solid-state battery cells in the case.

[0051] As an example, the case can include a first case and a second case. The first case and the second case are buckled so that a closed space is formed inside the case to accommodate the battery cell assembly. Here, closed means covered or closed, which can be sealed or unsealed. The first case can be a top cover or a bottom plate.

[0052] As an example, the case can include a top cover, a frame and a bottom plate. The top cover and the bottom plate are connected with the frame respectively, so that a closed space is formed inside the case to accommodate the battery cell assembly.

[0053] In some embodiments, the case can be part of the chassis structure of a vehicle. For example, part of the case can be at least part of the floor of the vehicle, or part of the case can be at least part of the cross beam and the longitudinal beam of the vehicle.

[0054] The technical solutions described in the embodiments of the present disclosure are applicable to various electric devices using solid-state battery cells and battery devices, such as mobile devices (e.g., mobile phones, tablet computers, notebook computers, etc.), electric vehicles (e.g., pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc. The solid-state battery cells and the battery devices are used to store or provide electric energy.

[0055] The contact between the electrode and the electrolyte sheet of the solid-state battery cell is solid-solid contact, and the ion transmission channel is less and the ion transmission is more difficult. Therefore, a mixed material including a positive electrode active material and a solid electrolyte material is usually used as the positive electrode.

[0056] At present, the solid-state electrolyte materials widely used in solid-state battery cells mainly include oxide solid-state electrolyte materials, polymer solid-state electrolyte materials and sulfide solid-state electrolyte materials. The oxide solid-state electrolyte material has a wide electrochemical window and good thermal stability, but its own ionic conductivity is low and there is an interface problem; the polymer solid-state electrolyte material has good ductility, but its own ionic conductivity is low; the sulfide solid-state electrolyte material has high ionic conductivity, but its own electrochemical window is narrow and oxidation stability is poor. Therefore, these materials are not suitable as solid-state electrolyte materials in high-voltage cathodes.

[0057] The halide solid electrolyte material can have high ionic conductivity and high oxidation stability, and thus can be better used in cathodes. At present, the halide solid electrolyte material is mostly concentrated in Li3MCl6 (M is a trivalent rare earth element, such as Li3InCl6, Li3YCl6, Li3HoCl6) and new halide oxide solid electrolyte materials represented by LiTaOCl4 and LiNbOCl4. Li3MCl6 has a wide electrochemical window, but the ionic conductivity is relatively low, usually less than 1 mS / cm. LiTaOCl4 and LiNbOCl4 have high ionic conductivity of more than 10 mS / cm and high oxidation stability, but the generation of byproduct hydrogen chloride gas often accompanies the ball milling process of this type of halide oxide solid electrolyte material, and the safety risk of the ball milling process is high. In addition, hydrogen chloride will corrode the equipment, so this type of halide oxide solid electrolyte material is not conducive to large-scale production.

[0058] Therefore, the present disclosure provides a halide solid electrolyte material and a cathode sheet containing the same, which is applied to a solid-state battery cell and can improve the cycle stability and rate performance of the solid-state battery cell.

[0059] The cathode sheet of the present disclosure includes a cathode active material and a halide solid electrolyte material.

[0060] The halide solid electrolyte material is amorphous, and the molecular formula of the halide solid electrolyte material is LiM 1 x M 2 y X6, M 1 including one or both of Ta and Nb, M 2 including one or more of a trivalent metal element and a tetravalent metal element, X including one or more of a halogen element, 0.5≤x<1, and LiM 1 x M 2 y X6 is electrically neutral.

[0061] The halide solid electrolyte material at the present stage is not stable to the sulfide solid electrolyte material, which will generate metal sulfide by-products, thereby increasing the interface impedance of the solid-state battery monomer.

[0062] The present disclosure adjusts the microstructure of the halide solid electrolyte material by doping one or more of trivalent metal elements and tetravalent metal elements at the Ta site and / or the Nb site of X6, and makes the halide solid electrolyte material amorphous, thereby improving the ionic conductivity and stability of the halide solid electrolyte material, especially the stability of the halide solid electrolyte material relative to the sulfide solid electrolyte material, so that the solid-state battery monomer has higher ion transport characteristics. The positive electrode sheet of the present disclosure is applied to the solid-state battery monomer, which can improve the cycle stability and rate performance of the solid-state battery monomer. In addition, the halide solid electrolyte material LiM 1 X6is doped with one or more of trivalent metal elements and tetravalent metal elements at the Ta site and / or the Nb site, and the halide solid electrolyte material is amorphous, which can adjust the microstructure of the halide solid electrolyte material, improve the ionic conductivity and stability of the halide solid electrolyte material, especially the stability of the halide solid electrolyte material relative to the sulfide solid electrolyte material, so that the solid-state battery monomer has higher ion transport characteristics. The positive electrode sheet of the present disclosure is applied to the solid-state battery monomer, which can improve the cycle stability and rate performance of the solid-state battery monomer. In addition, the halide solid electrolyte material LiM 1 x M 2 y X6is easy to produce in large scale.

[0063] 0.5≤x<1, for example, x can be 0.5, 0.52, 0.54, 0.56, 0.58, 0.6, 0.62, 0.64, 0.66, 0.68, 0.7, 0.72, 0.74, 0.76, 0.78, 0.8, 0.82, 0.84, 0.86, 0.88, 0.9, or a range composed of any of the above values.

[0064] Alternatively, 0.6≤x≤0.9, 0.62≤x≤0.9, 0.64≤x≤0.9, 0.66≤x≤0.9, 0.68≤x≤0.9, 0.7≤x≤0.9, 0.72≤x≤0.9, 0.74≤x≤0.9, 0.76≤x≤0.9, 0.78≤x≤0.9, 0.6≤x≤0.88, 0.62≤x≤0.88, 0.64≤x≤0.88, 0.66≤x≤0.88, 0.68≤x≤0.88, 0.7≤x≤0.88, 0.72≤x≤0.88, 0.74≤x≤0.88, 0.76≤x≤0.88, 0.78≤x≤0.88.

[0065] Thereby the ionic conductivity of the halide solid electrolyte material can be further improved, and the cycle stability and rate performance of the solid-state battery monomer can also be improved.

[0066] In some embodiments, M 1 may include Ta. The molecular formula of the halide solid electrolyte material is LiTa x M 2 yX6. Thus, the solid-state battery cell can have high ion transport characteristics, good cycle stability, and good rate performance.

[0067] In some embodiments, M 2 may include one or more of trivalent rare earth metal elements, tetravalent rare earth metal elements.

[0068] In some embodiments, M 2 may include one or more of Bi, Sb, As, Sc, Y, La, Pr, Nd, Eu, Gd, Tb, Ho, Er, Tm, Yb, Lu, Zr, Hf, Ce, Ge.

[0069] Optionally, M 2 may include one or more of Y, Zr, Hf.

[0070] In some embodiments, M 2 may be Zr.

[0071] Thus, the cycle stability and rate performance of the solid-state battery cell can be further improved.

[0072] In some embodiments, M 2 may include Zr and at least one of Bi, Sb, As, Sc, Y, La, Pr, Nd, Eu, Gd, Tb, Ho, Er, Tm, Yb, Lu, Hf, Ce, Ge. Optionally, the molar ratio of Zr element in M 2 elements is greater than or equal to 60%, optionally greater than or equal to 70%, greater than or equal to 75%, greater than or equal to 80%, greater than or equal to 85%, greater than or equal to 90%, greater than or equal to 95%.

[0073] Thus, the cycle stability and rate performance of the solid-state battery cell can be further improved.

[0074] In some embodiments, X can include one or more of Cl, Br, F.

[0075] In some embodiments, X can include Cl. The molecular formula of the halide solid-state electrolyte material is LiM 1 x M 2 y Cl6.

[0076] In some embodiments, X can include Cl and F, thus the stability of the halide solid-state electrolyte material can be improved, so that it can exist stably in air.

[0077] Optionally, the molecular formula of the halide solid-state electrolyte material can be LiM 1 xM 2 y Cl 6-z F z 0.1≤z≤0.5.

[0078] In some embodiments, X can include Cl and Br, which can improve the ionic conductivity of the halide solid-state electrolyte material.

[0079] Optionally, the molecular formula of the halide solid-state electrolyte material can be LiM 1 x M 2 y Cl 6-p Br p 0.1≤p≤3.

[0080] In some embodiments, X can include Cl, Br and F, which can improve the ionic conductivity of the halide solid-state electrolyte material, and also make it stable in air.

[0081] Optionally, the molecular formula of the halide solid-state electrolyte material can be LiM 1 x M 2 y Cl 6-p-z Br p F z 0.1≤p≤3, 0.1≤z≤0.5.

[0082] In some embodiments, the halide solid-state electrolyte material can have an ionic conductivity of 2 mS / cm-7 mS / cm at 25°C, such as 2 mS / cm, 2.2 mS / cm, 2.4 mS / cm, 2.6 mS / cm, 2.8 mS / cm, 3 mS / cm, 3.2 mS / cm, 3.4 mS / cm, 3.6 mS / cm, 3.8 mS / cm, 4 mS / cm, 4.2 mS / cm, 4.4 mS / cm, 4.6 mS / cm, 4.8 mS / cm, 5 mS / cm, 5.2 mS / cm, 5.4 mS / cm, 5.6 mS / cm, 5.8 mS / cm, 6 mS / cm, 6.2 mS / cm, 6.4 mS / cm, 6.6 mS / cm, 6.8 mS / cm, 7 mS / cm, or a range defined by any of the foregoing values. Optionally, the halide solid-state electrolyte material can have an ionic conductivity of 2.6 mS / cm-7 mS / cm, 2.8 mS / cm-7 mS / cm at 25°C.

[0083] In some embodiments, the mass ratio of the positive electrode active material to the halide solid electrolyte material can be 99:1 to 60:40, for example, can be 99:1, 98:2, 97:3, 96:4, 95:5, 94:6, 93:7, 92:8, 91:9, 90:10, 89:11, 88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:33, 66:34, 65:35, 64:36, 63:37, 62:38, 61:39, 60:40, or a range composed of any of the above values.

[0084] The mass ratio of the positive electrode active material to the halide solid electrolyte material in the above range can make the solid-state battery monomer have high energy density and high ion transport characteristics.

[0085] Optionally, the mass ratio of the positive electrode active material to the halide solid electrolyte material can be 95:5 to 60:40, 90:10 to 60:40, 85:15 to 60:40, 95:5 to 65:35, 90:10 to 65:35, 85:15 to 65:35.

[0086] In some embodiments, the positive electrode active material and the halide solid electrolyte material in the positive electrode sheet can be in a mixed state.

[0087] In some embodiments, the halide solid electrolyte material in the positive electrode sheet can be coated on at least part of the surface of the positive electrode active material.

[0088] By coating the halide solid electrolyte material on at least part of the surface of the positive electrode active material, the crystal structure of the positive electrode active material can be stabilized, and the ion transport characteristics, the cycle stability, and the rate performance of the solid-state battery monomer can be further improved.

[0089] Optionally, the positive electrode active material and the halide solid electrolyte material can be mixed, and then heated at 200°C-250°C for 4h-6h to coat the halide solid electrolyte material on at least part of the surface of the positive electrode active material. Optionally, the positive electrode active material and the halide solid electrolyte material can be mixed by using a mortar or a ball milling tank. Optionally, the mixing time can be 20min-60min. Optionally, the ball milling rotation speed can be 100pm-200rpm.

[0090] In some embodiments, the halide solid-state electrolyte material can coat at least part of the surface of the positive electrode active material, and the mass ratio of the positive electrode active material to the halide solid-state electrolyte material can be 99:1 to 85:15, for example, can be 99:1, 98:2, 97:3, 96:4, 95:5, 94:6, 93:7, 92:8, 91:9, 90:10, 89:11, 88:12, 87:13, 86:14, 85:15, or a range composed of any of the above values. The mass ratio of the positive electrode active material to the halide solid-state electrolyte material in the above range can enable the solid-state battery cell to have high energy density and high ion transport characteristics. Alternatively, the mass ratio of the positive electrode active material to the halide solid-state electrolyte material can be 98:2 to 85:15, 96:4 to 85:15, 98:2 to 88:12, 96:4 to 88:12, 98:2 to 90:10, 96:4 to 90:10.

[0091] In some embodiments, the halide solid-state electrolyte material can have a volume distribution particle size Dv90 of 0.5 μm-3 μm.

[0092] In some embodiments, the positive electrode active material can have a volume distribution particle size Dv50 of 3 μm-5 μm.

[0093] This facilitates the halide solid-state electrolyte material coating the surface of the positive electrode active material.

[0094] Dv50 and Dv90 respectively represent the particle size corresponding to the cumulative volume distribution percentage of 50% and 90%, which can be tested by a laser particle size analyzer according to GB / T 19077-2016. During the test, 1 g of the sample to be tested can be taken into a clean beaker, 20 ml of deionized water is added, and ultrasonic treatment is performed at 53 KHz / 120 W for 5 min to ensure complete dispersion of the sample. After cleaning the light path system, the background is automatically tested. The sample solution after ultrasonic treatment is stirred to make it uniformly dispersed, and then placed in the sample cell as required to start measuring the particle size. The testing instrument can be a MasterSizer 3000 laser particle size analyzer.

[0095] In some embodiments, the positive electrode active material can include one or more of lithium transition metal oxides and modified materials thereof, lithium-containing phosphates and modified materials thereof, lithium titanate, sulfur, selenium, and tellurium.

[0096] Alternatively, examples of the lithium transition metal oxide can include, but are not limited to, one or more of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, and lithium-rich manganese-based materials.

[0097] Optionally, examples of lithium-containing phosphates can include, but are not limited to, one or more of lithium iron phosphate, a composite of lithium iron phosphate and carbon, lithium manganese phosphate, a composite of lithium manganese phosphate and carbon, lithium manganese iron phosphate, a composite of lithium manganese iron phosphate and carbon.

[0098] In some embodiments, to further boost the energy density of the solid-state battery cell, the cathode active material can include one or more of lithium transition metal oxides of the general formula Li a Ni b Co c M d O e A f 0.8≤a≤1.2, 0.5≤b<1, 0<c<1, 0<d<1, 1≤e≤2, 0≤f≤1, M can include one or more of Mn, Al, Zr, Zn, Cu, Cr, Mg, Fe, V, Ti, and B, and A can include one or more of N, F, S, and Cl.

[0099] As examples, the cathode active material can include, but is not limited to, LiCoO2, LiNiO2, LiMnO2, LiMn2O4, LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2(simplified as NCM333), LiNi 0.5 Co 0.2 Mn 0.3 O2(simplified as NCM523), LiNi 0.5 Co 0.25 Mn 0.25 O2(simplified as NCM211), LiNi 0.6 Co 0.2 Mn 0.2 O2(simplified as NCM622), LiNi 0.8 Co 0.1 Mn 0.1 O2(simplified as NCM811), LiNi 0.83 Mn 0.08 Co 0.07 O2(simplified as Ni83), LiNi 0.90 Mn 0.05 Co 0.05 O2(simplified as Ni90), LiNi 0.94 Mn 0.03 Co 0.03 O2(simplified as Ni94), LiNi 0.96 Co 0.02 Mn 0.02 O2(simplified as Ni96), LiNi 0.80 Co0.15 Al 0.05 O2, LiFePO4, LiMnPO4, and their respective modified materials.

[0100] The modified material of each of the above positive electrode active materials can be a doping modification and / or a surface coating modification of the positive electrode active material.

[0101] The solid-state battery cell will be accompanied by Li deintercalation and consumption during charging and discharging, and the molar content of Li is different when the solid-state battery cell is discharged to different states. In the enumeration of the positive electrode active material in the present disclosure, the molar content of Li is the initial state of the material, i.e., the state before feeding. When the positive electrode active material is applied to the solid-state battery cell, the molar content of Li will change after charging and discharging cycles. In the enumeration of the positive electrode active material in the present disclosure, the molar content of O is only the theoretical state value, and the release of oxygen from the crystal lattice will cause the molar content of O to change, and the actual molar content of O will also appear to float.

[0102] In some embodiments, the positive electrode sheet can also include a positive electrode conductive agent, which can include but is not limited to one or more of super conductive carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, carbon nanofibers, and vapor grown carbon fiber (VGCF).

[0103] In some embodiments, the positive electrode sheet can include a positive electrode binder, or can not include a positive electrode binder, which can be adjusted according to the type of solid-state battery cell and the preparation process.

[0104] Optionally, the positive electrode binder can include but is not limited to one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, styrene butadiene rubber (SBR), water-soluble unsaturated resin SR-1B, methyl vinyl silicone rubber, nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), thermoplastic styrene butadiene rubber (SBS), isoprene rubber, butadiene rubber (BR), ethyl cellulose, fluororubber, and acrylate rubber.

[0105] In some embodiments, the positive electrode sheet can also include a positive electrode current collector and a positive electrode active material layer on at least one surface of the positive electrode current collector, and the positive electrode active material layer includes the above-mentioned positive electrode active material and halide solid-state electrolyte material.

[0106] In some embodiments, the positive electrode active material layer can also include a positive electrode conductive agent. Optionally, the positive electrode conductive agent can include but is not limited to one or more of super conductive carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, carbon nanofibers, and vapor grown carbon fiber (VGCF).

[0107] In some embodiments, the positive active material layer can further include a positive electrode binder. Optionally, the positive electrode binder can include, but is not limited to, one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, styrene butadiene rubber (SBR), water-soluble unsaturated resin SR-1B, methyl vinyl silicone rubber, nitrile butadiene rubber (NBR), hydrogenated nitrile butadiene rubber (HNBR), thermoplastic styrene butadiene rubber (SBS), isoprene rubber, butadiene rubber (BR), ethyl cellulose, fluoro rubber, and acrylate rubber.

[0108] In some embodiments, the positive current collector can employ a metal foil or a composite current collector. As an example of the metal foil, a stainless steel foil, a carbon-coated aluminum foil, or an aluminum foil can be employed. The composite current collector can include a polymer material base layer and a metal material layer formed on at least one surface of the polymer material base layer. As an example, the metal material can include, but is not limited to, one or more of aluminum, an aluminum alloy, nickel, a nickel alloy, titanium, a titanium alloy, silver, and a silver alloy. As an example, the polymer material base layer can include, but is not limited to, one or more of polypropylene, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), and polyethylene.

[0109] The positive electrode sheet can be prepared by a dry process or by a wet process.

[0110] The present disclosure also provides a method of preparing a halide solid-state electrolyte material, which can prepare the halide solid-state electrolyte material of the present disclosure.

[0111] The method of preparing the halide solid-state electrolyte material includes the following steps: in an inert atmosphere, ball-milling a halide of M 1 , a halide of M 2 , and a halide of Li in a stoichiometric ratio to obtain an amorphous LiM 1 x M 2 y X6, M 1 includes one or both of Ta and Nb, M 2 includes one or more of a trivalent metal element and a tetravalent metal element, X includes one or more of a halogen element, 0.5≤x<1, and LiM 1 x M 2 y X6is electrically neutral.

[0112] The ball-milling method is employed and M 1The ratio of M 2 The amorphous halide solid-state electrolyte material LiM 1 x M 2 y X6, and the formation of a crystal halide with high diffraction peak intensity in the product can be avoided.

[0113] In some embodiments, the rotation speed of the ball mill can be 400 rpm-600 rpm.

[0114] In some embodiments, the ball milling time can be 20 h-180 h.

[0115] In some embodiments, the ball milling medium can include zirconium oxide balls. Optionally, the size of the zirconium oxide balls can be 0.2 mm-10 mm.

[0116] In some embodiments, the ball-to-material ratio of the ball milling process can be 30:1 to 60:1.

[0117] In some embodiments, the inert atmosphere can include one or more of nitrogen, argon, and helium.

[0118] In some embodiments, the method of preparing the halide solid-state electrolyte material further includes a step of wet milling after the ball milling process. Thereby, the particle size of the halide solid-state electrolyte material can be adjusted, and it is facilitated to uniformly coat the halide solid-state electrolyte material on the surface of the positive electrode active material.

[0119] The present disclosure also provides a solid-state battery cell, which includes a negative electrode sheet, an electrolyte sheet, and a positive electrode sheet provided by the present disclosure, the electrolyte sheet being located between the negative electrode sheet and the positive electrode sheet.

[0120] The solid-state battery cell of the present disclosure can be a button cell, a die cell, a hard-shell cell, a soft-pack cell, or the like.

[0121] [Electrolyte sheet]

[0122] The electrolyte sheet can be prepared by a dry process or by a wet process.

[0123] In some embodiments, the electrolyte sheet includes a solid-state electrolyte material. The solid-state electrolyte material can employ a material known in the art. Optionally, the solid-state electrolyte material can include one or more of a sulfide solid-state electrolyte material, a halide solid-state electrolyte material, and an oxide solid-state electrolyte material. More optionally, the solid-state electrolyte material can include a sulfide solid-state electrolyte material.

[0124] In some embodiments, the sulfide solid-state electrolyte material can include one or more of a argyrodite-type, LGPS-type, and lithium sulfide-pentasulfide phosphorus complex-type sulfide solid-state electrolyte material.

[0125] Optionally, in some embodiments, the argyrodite-type sulfide solid-state electrolyte material can include a material of a chemical formula of Li 6±s P 1-j A j S 5±s-t B t D 1±s , 0≤j<1, 0≤t<1, 0≤s<1, A includes one or more elements of Ge, Si, Sn, and Sb, B includes one or more elements of O, Se, and Te, and D includes one or more elements of Cl, Br, I, and F.

[0126] Optionally, in some embodiments, the LGPS-type sulfide solid-state electrolyte material can include a material of a chemical formula of Li 10±δ5 Ge 1-g G g P 2-q Q q S 12-w W w , 0≤δ5<1, 0≤g≤1, 0≤q≤2, 0≤w<1, G includes one or two elements of Si and Sn, Q includes Sb, and W includes one or more elements of O, Se, Te, Cl, Br, I, and F.

[0127] Optionally, in some embodiments, the lithium sulfide diphosphorous pentasulfide composite-type sulfide solid-state electrolyte material can include a material of a chemical formula of (100-u-v)Li2S·uP2S5·vM m N n , 0<u<100, 0≤v<100, 0≤u+v<100, 0≤m<4, 0≤n<6, M includes one or more elements of Li, B, Ge, Si, Sn, and Sb, and N includes one or more elements of S, Se, Te, O, Cl, Br, I, and F.

[0128] As an example, the sulfide solid-state electrolyte material can include one or more of Li6PS5Cl, Li6PS5Br, Li 10 GeP2S 12 , Li3PS4, Li7P3S 11 .

[0129] In some embodiments, the electrolyte sheet can or can not include a binder, which can be adjusted according to the type of solid-state battery cell and the preparation process.

[0130] Optionally, the binder can include, but is not limited to, one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene-hexafluoropropylene-tetrafluoroethylene terpolymer, vinylidene-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, styrene butadiene rubber (SBR), water-soluble unsaturated resin SR-1B, methyl vinyl silicone rubber, nitrile butadiene rubber (NBR), hydrogenated nitrile butadiene rubber (HNBR), thermoplastic styrene butadiene rubber (SBS), isoprene rubber, butadiene rubber (BR), ethyl cellulose, fluororubber, and acrylate rubber.

[0131] [Anode sheet]

[0132] The anode sheet can be prepared by a dry process or by a wet process.

[0133] In some embodiments, the anode sheet can include one or more of graphite, graphene, carbon nanotubes, meso-phase carbon microbeads, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, metal oxides, lithium, lithium alloys, lithium composites.

[0134] Optionally, the carbon-based material can include, but is not limited to, one or more of carbon powder, natural graphite, artificial graphite, meso-phase carbon microbeads, soft carbon, and hard carbon.

[0135] Optionally, the silicon-based material can include, but is not limited to, one or more of nano-silicon powder, micro-silicon powder, silicon oxide, silicon-carbon composite, silicon-nitrogen composite, and silicon alloy material.

[0136] Optionally, the tin-based material can include, but is not limited to, one or more of elemental tin, tin oxide, and tin alloy material.

[0137] Optionally, the metal oxide can include, but is not limited to, one or more of TiO2, MoO2, In2O3, Al2O3, Cu2O, VO2, Ga2O3, Sb2O5, and Bi2O5.

[0138] Optionally, the other elements in the lithium alloy can include one or more of In, Mg, Al, Zn, Sn, Ag, Au, Ga, Pt, and Fe, for example, can be Li-In alloy, Li-Mg alloy, Li-Al alloy, Li-Zn alloy, Li-Fe alloy, etc.

[0139] In some embodiments, the negative electrode sheet can further include a negative electrode binder, which can include, but is not limited to, one or more of styrene butadiene rubber (SBR), water-soluble unsaturated resin SR-1B, polyacrylic acid, polymethacrylic acid, sodium polyacrylate, polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), carboxymethyl chitosan (CMCS), methyl vinyl silicone rubber, nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), sodium carboxymethyl cellulose (CMC), thermoplastic styrene butadiene rubber (SBS), isoprene rubber, butadiene rubber (BR), ethyl cellulose, fluoro rubber, and acrylate rubber.

[0140] In some embodiments, the negative electrode sheet can further include a negative electrode conductive agent, which can or can not be included, and can be adjusted according to the type of solid-state battery cell and the preparation process.

[0141] Optionally, the negative electrode conductive agent can include, but is not limited to, one or more of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, carbon nanofibers, and vapor grown carbon fiber (VGCF).

[0142] In some embodiments, the negative electrode sheet can further include a solid-state electrolyte material, which can or can not be included. The solid-state electrolyte material can be a material known in the art. Optionally, the solid-state electrolyte material can include, but is not limited to, one or more of sulfide solid-state electrolyte material, halide solid-state electrolyte material, and oxide solid-state electrolyte material.

[0143] In some embodiments, the negative electrode sheet can include a negative electrode current collector and a negative electrode active material layer on at least one surface of the negative electrode current collector, and the negative electrode active material layer can include one or more of graphite, graphene, carbon nanotubes, mesocarbon microbeads, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, metal oxides, and lithium composite materials.

[0144] In some embodiments, the negative electrode active material layer can further include a negative electrode binder. Optionally, the negative electrode binder can include, but is not limited to, one or more of styrene butadiene rubber (SBR), water-soluble unsaturated resin SR-1B, polyacrylic acid, polymethacrylic acid, sodium polyacrylate, polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), carboxymethyl chitosan (CMCS), methyl vinyl silicone rubber, nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), sodium carboxymethyl cellulose (CMC), thermoplastic styrene butadiene rubber (SBS), isoprene rubber, butadiene rubber (BR), ethyl cellulose, fluoro rubber, and acrylate rubber.

[0145] In some embodiments, the negative active material layer can further include a negative conductive agent. Optionally, the negative conductive agent can include, but is not limited to, one or more of super P, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, carbon nanofibers, and vapor grown carbon fiber (VGCF).

[0146] In some embodiments, the negative active material layer can further include a solid-state electrolyte material or can not include a solid-state electrolyte material. The solid-state electrolyte material can employ materials known in the art. Optionally, the solid-state electrolyte material can include, but is not limited to, one or more of sulfide solid-state electrolyte material, halide solid-state electrolyte material, and oxide solid-state electrolyte material.

[0147] In some embodiments, the negative electrode sheet can include a negative current collector and a lithium-based metal layer on at least one surface of the negative current collector, the lithium-based metal layer including lithium or a lithium alloy. Optionally, the other elements in the lithium alloy can include one or more of In, Mg, Al, Zn, Sn, Ag, Au, Ga, Pt, and Fe, such as Li-In alloy, Li-Mg alloy, Li-Al alloy, Li-Zn alloy, Li-Fe alloy, etc.

[0148] In some embodiments, the negative current collector can include a metal foil, a three-dimensional porous current collector, or a composite current collector. As an example of the metal foil, stainless steel foil, copper foil, copper alloy foil, nickel foil, nickel alloy foil, aluminum foil, and aluminum alloy foil can be employed. As an example of the three-dimensional porous current collector, copper mesh, nickel mesh, aluminum mesh, foamed copper, foamed nickel, and foamed aluminum can be employed. The composite current collector can include a polymer material base layer and a metal material layer formed on at least one surface of the polymer material base layer. As an example, the metal material can include, but is not limited to, one or more of copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver, and silver alloy. As an example, the polymer material base layer can include, but is not limited to, one or more of polypropylene, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene, and polyethylene.

[0149] In some embodiments, the negative electrode sheet can be a lithium sheet or a lithium alloy sheet. Optionally, the other elements in the lithium alloy can include one or more of In, Mg, Al, Zn, Sn, Ag, Au, Ga, Pt, and Fe, such as Li-In alloy, Li-Mg alloy, Li-Al alloy, Li-Zn alloy, Li-Fe alloy, etc.

[0150] In some embodiments, the solid-state battery cell further comprises an outer package. The outer package can be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc. The outer package can also be a soft package, such as a pouch soft package. The soft package can be made of plastic, such as one or more of aluminum-plastic film, polypropylene, polybutylene terephthalate (PBT), and polybutylene succinate (PBS).

[0151] [Preparation method]

[0152] The preparation method of the solid-state battery cell is known, for example, the assembly methods of the solid-state battery cell include but are not limited to button cell, mold cell, hard shell cell, soft package cell, etc.

[0153] Embodiments

[0154] The following examples more specifically describe the disclosure disclosed in the present disclosure, which are only used for illustrative explanation, and various modifications and changes within the scope of the disclosure disclosed in the present disclosure are obvious to those skilled in the art. Unless otherwise stated, all parts, percentages and ratios reported in the following examples are based on mass, and all reagents used in the examples are commercially available or synthesized according to conventional methods, and can be used directly without further treatment, and the instruments used in the examples are commercially available.

[0155] Example 1

[0156] Preparation of halide solid electrolyte material

[0157] In an argon atmosphere, TaCl5, ZrCl4, LiCl, LiF were put into a zirconia ball mill jar according to the stoichiometric ratio for high-energy ball milling, and a halide solid electrolyte material LiTa 0.9 Zr 0.125 Cl 5.9 F 0.1 The ball milling speed was 600 rpm, and the ball milling time was 40 h.

[0158] Preparation of solid-state battery cell

[0159] The solid-state battery cell was assembled based on the mold cell. First, 100 mg of Li6PS5Cl was added to the mold, and the electrolyte sheet was obtained by compacting under a pressure of 125 MPa; 15 mg of mixed positive electrode powder and Li-In alloy were added on both sides of the electrolyte sheet as the positive electrode and the negative electrode, respectively, and the mold cell was pressed under a pressure of 500 MPa, and the pressure was maintained for 5 min to obtain the solid-state battery cell.

[0160] The mixed positive electrode powder was composed of positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1O2, halide solid-state electrolyte material LiTa 0.9 Zr 0.125 Cl 5.9 F 0.1 , positive electrode conductive agent vapor grown carbon fiber (VGCF), and the mass ratio of the three is 70:27:3.

[0161] Example 2

[0162] Preparation of halide solid-state electrolyte material

[0163] In an argon atmosphere, TaCl5, ZrCl4, LiCl, and LiF were put into a zirconium oxide ball mill jar according to the stoichiometric ratio for high-energy ball milling, and halide solid-state electrolyte material LiTa 0.9 Zr 0.125 Cl 5.9 F 0.1 The ball milling speed was 600 rpm, and the ball milling time was 40 h.

[0164] Preparation of solid-state battery monomer

[0165] The positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O2, solid-state electrolyte material LiTa 0.9 Zr 0.125 Cl 5.9 F 0.1 According to the mass ratio 90:10, mix uniformly and place in the ball mill jar, ball mill mixing at the speed of 200 rpm for 30 min, then heat at 200℃ for 5h, get the positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O2with halide solid-state electrolyte material coating. The composition of the mixed positive electrode powder is the positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O2, positive electrode conductive agent vapor grown carbon fiber (VGCF), and the mass ratio of the two is 97:3.

[0166] The solid-state battery monomer was assembled based on the mold battery. First, 100mg Li6PS5Cl was added to the mold and compacted with a pressure of 125MPa to obtain an electrolyte sheet; 15mg of mixed positive electrode powder and Li-In alloy were added on both sides of the electrolyte sheet as the positive electrode and the negative electrode, respectively, and the mold battery was pressed with a pressure of 500MPa for 5min to obtain the solid-state battery monomer.

[0167] Example 3

[0168] Preparation of halide solid electrolyte material

[0169] TaCl5, ZrCl4, LiCl, LiF were put into a zirconia ball mill jar in a stoichiometric ratio for high-energy ball milling in an argon atmosphere to obtain halide solid electrolyte material LiTa 0.8 Zr 0.25 Cl 5.9 F 0.1 The ball milling speed was 600 rpm, and the ball milling time was 40 h.

[0170] Preparation of solid-state battery monomer

[0171] The positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O2, the solid electrolyte material LiTa 0.8 Zr 0.25 Cl 5.9 F 0.1 The positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O2 with a halide solid electrolyte material coating layer was obtained by mixing the two in a mass ratio of 70:30, placing them in a ball mill, ball milling at a speed of 200 rpm for 30 min, and then heating at 200°C for 5 h. 0.8 Co 0.1 Mn 0.1 O2, and positive electrode conductive agent vapor grown carbon fiber (VGCF) in a mass ratio of 97:3.

[0172] The solid-state battery monomer was assembled based on a mold battery. First, 100 mg of Li6PS5Cl was added to the mold, and the electrolyte sheet was obtained by compacting under a pressure of 125 MPa; 15 mg of mixed positive electrode powder and Li-In alloy were added on both sides of the electrolyte sheet as the positive electrode and the negative electrode, respectively, and the mold battery was pressed under a pressure of 500 MPa for 5 min to obtain the solid-state battery monomer.

[0173] Example 4

[0174] Preparation of halide solid electrolyte material

[0175] TaCl5, ZrCl4, LiCl, LiF were put into a zirconia ball mill jar in a stoichiometric ratio for high-energy ball milling in an argon atmosphere to obtain halide solid electrolyte material LiTa 0.7 Zr 0.375 Cl 5.9 F 0.1The ball milling speed was 600 rpm, and the ball milling time was 40 h.

[0176] Preparation of a solid-state battery cell

[0177] The positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O2, the solid-state electrolyte material LiTa 0.7 Zr 0.375 Cl 5.9 F 0.1 The positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O2 coated with the halide solid-state electrolyte material was obtained by mixing the positive electrode powder in a mass ratio of 70:30, placing it in a ball mill, ball milling at a speed of 200 rpm for 30 min, and then heating at 200°C for 5 h. 0.8 Co 0.1 Mn 0.1 O2, the positive electrode conductive agent vapor-grown carbon fiber (VGCF), and the mass ratio of the two was 97:3.

[0178] The solid-state battery cell was assembled based on a mold battery. First, 100 mg of Li6PS5Cl was added to the mold, and the electrolyte sheet was obtained by compacting under a pressure of 125 MPa; 15 mg of the mixed positive electrode powder and Li-In alloy were added on both sides of the electrolyte sheet as the positive electrode and the negative electrode, respectively, and the mold battery was pressed under a pressure of 500 MPa for 5 min to obtain the solid-state battery cell.

[0179] Example 5

[0180] Preparation of a halide solid-state electrolyte material

[0181] In an argon atmosphere, TaCl5, ZrCl4, LiCl, and LiF were put into a zirconia ball mill jar according to the stoichiometric ratio for high-energy ball milling to obtain the halide solid-state electrolyte material LiTa 0.5 Zr 0.625 Cl 5.9 F 0.1 The ball milling speed was 600 rpm, and the ball milling time was 40 h.

[0182] Preparation of a solid-state battery cell

[0183] The positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O2, the solid-state electrolyte material LiTa 0.5 Zr 0.625Cl 5.9 F 0.1 The positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O2, the solid-state electrolyte material LiTa 0.8 Co 0.1 Mn 0.1 O2, and the positive electrode conductive agent vapor grown carbon fiber (VGCF) were mixed in a mass ratio of 97:3.

[0184] The solid-state battery monomer was assembled based on a mold battery. 100 mg of Li6PS5Cl was added to the mold and compacted under a pressure of 125 MPa to obtain an electrolyte sheet; 15 mg of the mixed positive electrode powder and Li-In alloy were added to the two sides of the electrolyte sheet as the positive electrode and the negative electrode, respectively, and the mold battery was pressed under a pressure of 500 MPa for 5 min to obtain the solid-state battery monomer.

[0185] Example 6

[0186] Preparation of the halide solid-state electrolyte material

[0187] In an argon atmosphere, TaCl5, YCl3, LiCl, LiBr, and LiF were put into a zirconia ball mill jar according to the stoichiometric ratio for high-energy ball milling to obtain the halide solid-state electrolyte material LiTa 0.7 Y 0.5 Cl3Br 2.9 F 0.1 The ball milling speed was 600 rpm, and the ball milling time was 40 h.

[0188] Preparation of the solid-state battery monomer

[0189] The positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O2, the solid-state electrolyte material LiTa 0.7 Y 0.5 Cl3Br 2.9 F 0.1 The positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1O2, cathode conductive agent vapor grown carbon fiber (VGCF), and the mass ratio of the two is 97:3. 0.8 Co 0.1 Mn 0.1 O2, cathode conductive agent vapor grown carbon fiber (VGCF), and the mass ratio of the two is 97:3.

[0190] The solid-state battery monomer was assembled based on a mold battery. First, 100 mg of Li6PS5Cl was added to the mold and compacted under a pressure of 125 MPa to obtain an electrolyte sheet; 15 mg of mixed cathode powder and Li-In alloy were added on both sides of the electrolyte sheet as the positive electrode and the negative electrode, respectively, and the mold battery was pressed under a pressure of 500 MPa for 5 min to obtain a solid-state battery monomer.

[0191] Example 7

[0192] Preparation of halide solid-state electrolyte material

[0193] In an argon atmosphere, TaCl5, YCl3, LiCl, and LiF were added to a zirconia ball mill jar in a stoichiometric ratio for high-energy ball milling, and a halide solid-state electrolyte material LiTa 0.7 Y 0.5 Cl 5.9 F 0.1 The ball milling speed was 600 rpm, and the ball milling time was 40 h.

[0194] Preparation of solid-state battery monomer

[0195] The positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O2, solid-state electrolyte material LiTa 0.7 Y 0.5 Cl 5.9 F 0.1 The positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O2, cathode conductive agent vapor grown carbon fiber (VGCF), and the mass ratio of the two is 97:3. 0.8 Co 0.1 Mn 0.1 O2, cathode conductive agent vapor grown carbon fiber (VGCF), and the mass ratio of the two is 97:3.

[0196] The solid-state battery monomer was assembled based on a mold battery. First, 100 mg of Li6PS5Cl was added to the mold and compacted with a pressure of 125 MPa to obtain an electrolyte sheet; 15 mg of mixed positive electrode powder and Li-In alloy were added to both sides of the electrolyte sheet as the positive electrode and the negative electrode, respectively, and the mold battery was pressed with a pressure of 500 MPa, and the pressure was maintained for 5 min to obtain the solid-state battery monomer.

[0197] Example 8

[0198] Preparation of halide solid electrolyte material

[0199] In an argon atmosphere, TaCl5, YCl3, and LiCl were put into a zirconia ball mill jar according to the stoichiometric ratio for high-energy ball milling to obtain a halide solid electrolyte material LiTa 0.7 Y 0.5 Cl6. The ball milling speed was 600 rpm, and the ball milling time was 40 h.

[0200] Preparation of solid-state battery monomer

[0201] The positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O2, the solid electrolyte material LiTa 0.7 Y 0.5 Cl6 were mixed uniformly according to a mass ratio of 70:30 and placed in a ball mill, and ball milling was performed at a speed of 200 rpm for 30 min, followed by heating at 200°C for 5 h to obtain the positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O2 coated with a halide solid electrolyte material. The mixed positive electrode powder was composed of the positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O2 coated with a halide solid electrolyte material and the positive electrode conductive agent vapor-grown carbon fiber (VGCF) at a mass ratio of 97:3.

[0202] The solid-state battery monomer was assembled based on a mold battery. First, 100 mg of Li6PS5Cl was added to the mold and compacted with a pressure of 125 MPa to obtain an electrolyte sheet; 15 mg of mixed positive electrode powder and Li-In alloy were added to both sides of the electrolyte sheet as the positive electrode and the negative electrode, respectively, and the mold battery was pressed with a pressure of 500 MPa, and the pressure was maintained for 5 min to obtain the solid-state battery monomer.

[0203] Comparative Example 1

[0204] The solid-state battery monomer was assembled based on a mold battery. First, 100 mg of Li6PS5Cl was added to the mold and compacted with a pressure of 125 MPa to obtain an electrolyte sheet; 15 mg of mixed positive electrode powder and Li-In alloy were added to both sides of the electrolyte sheet as the positive electrode and the negative electrode, respectively, and the mold battery was pressed with a pressure of 500 MPa, and the pressure was maintained for 5 min to obtain a solid-state battery monomer.

[0205] The mixed positive electrode powder was composed of positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O2, halide solid electrolyte material LiTaCl6, positive electrode conductive agent vapor grown carbon fiber (VGCF), and the mass ratio of the three was 70:27:3.

[0206] Comparative Example 2

[0207] Preparation of halide solid electrolyte material

[0208] TaCl5, ZrCl4, LiCl, and LiF were put into a zirconia ball mill jar according to the stoichiometric ratio for high-energy ball milling to obtain halide solid electrolyte material Li 1.6 Ta 0.4 Zr 0.6 Cl 5.9 F 0.1 The ball milling speed was 600 rpm, and the ball milling time was 40 h.

[0209] Preparation of solid-state battery monomer

[0210] The solid-state battery monomer was assembled based on a mold battery. First, 100 mg of Li6PS5Cl was added to the mold and compacted with a pressure of 125 MPa to obtain an electrolyte sheet; 15 mg of mixed positive electrode powder and Li-In alloy were added to both sides of the electrolyte sheet as the positive electrode and the negative electrode, respectively, and the mold battery was pressed with a pressure of 500 MPa, and the pressure was maintained for 5 min to obtain a solid-state battery monomer.

[0211] The mixed positive electrode powder was composed of positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O2, halide solid electrolyte material Li 1.6 Ta 0.4 Zr 0.6 Cl 5.9 F 0.1 , positive electrode conductive agent vapor grown carbon fiber (VGCF), and the mass ratio of the three was 70:27:3.

[0212] Performance test

[0213] (1) Crystal form testing of halide solid electrolyte materials

[0214] XRD analysis was performed on halide solid electrolyte material powder samples to qualitatively determine whether the halide solid electrolyte material is crystalline or amorphous. The testing range was 10°–90°, the scanning speed was 3° / min, and an argon atmosphere was maintained throughout the testing process. The testing instrument was a Bruker D8 X-ray diffractometer.

[0215] (2) Ionic conductivity testing of halide solid electrolyte materials

[0216] The test temperature was 25℃. 100 mg of halide solid electrolyte material was added to a mold battery, pressurized, and assembled into a lithium-indium symmetric battery. The ionic conductivity of the prepared halide solid electrolyte material was then tested using electrochemical impedance spectroscopy (EIS) on an Autolab workstation, with a test frequency range of 10 Hz. 6 -10 -2 The Hz value and voltage are 10mV. The ionic conductivity of the halide solid electrolyte material is calculated based on the impedance value and the Arrhenius equation.

[0217] (3) First-round coulomb efficiency test

[0218] At 25°C, solid-state battery cells were charged to 4.3V (vs. Li) at a current density of 0.1C. + / Li), let stand for 10 minutes, then discharge at a current density of 0.1C to 2.8V (vs. Li). + / Li), to obtain the first-cycle charge specific capacity and the first-cycle discharge specific capacity. First-cycle coulombic efficiency (%) = first-cycle discharge specific capacity / first-cycle charge specific capacity × 100%.

[0219] (4) Cyclic performance test

[0220] At 25°C, the solid-state battery cell was first charged to 4.3V (vs. Li) at a current density of 0.1C. + / Li), let stand for 10 minutes, then discharge at a current density of 0.1C to 2.8V (vs. Li). + / Li), cycle charge and discharge 2 times; then charge the solid-state battery cell to 4.3V (vs. Li) at a current density of 0.33C. + / Li), let stand for 10 minutes, then discharge at a current density of 0.33C to 2.8V (vs. Li). + / Li), the discharge specific capacity at this time is recorded as C1. The solid-state battery cell is cycled 100 times at a current density of 0.33C, and the discharge specific capacity at this time is recorded as C2.

[0221] Capacity retention rate of the solid-state battery cell after 100 cycles = C2 / C1 x 100%.

[0222] (5) Rate performance test

[0223] The solid-state battery cell was first charged to 4.3 V (vs. Li + / Li) at a current density of 0.1 C at 25 °C, rested for 10 min, and then discharged to 2.8 V (vs. Li + / Li) at a current density of 0.1 C, cycled for 5 times, and the obtained capacity was recorded as the specific discharge capacity at a rate of 0.1 C.

[0224] The solid-state battery cell was then charged to 4.3 V (vs. Li + / Li) at a current density of 0.2 C at 25 °C, rested for 10 min, and then discharged to 2.8 V (vs. Li + / Li) at a current density of 0.2 C, cycled for 5 times, and the obtained capacity was recorded as the specific discharge capacity at a rate of 0.2 C.

[0225] The solid-state battery cell was then charged to 4.3 V (vs. Li + / Li) at a current density of 0.5 C at 25 °C, rested for 10 min, and then discharged to 2.8 V (vs. Li + / Li) at a current density of 0.5 C, cycled for 5 times, and the obtained capacity was recorded as the specific discharge capacity at a rate of 0.5 C.

[0226] The solid-state battery cell was then charged to 4.3 V (vs. Li + / Li) at a current density of 1 C at 25 °C, rested for 10 min, and then discharged to 2.8 V (vs. Li + / Li) at a current density of 1 C, cycled for 5 times, and the obtained capacity was recorded as the specific discharge capacity at a rate of 1 C.

[0227] The solid-state battery cell was then charged to 4.3 V (vs. Li + / Li) at a current density of 2 C at 25 °C, rested for 10 min, and then discharged to 2.8 V (vs. Li + / Li) at a current density of 2 C, cycled for 5 times, and the obtained capacity was recorded as the specific discharge capacity at a rate of 2 C.

[0228] The solid-state battery cell was then charged to 4.3 V (vs. Li + / Li) at a current density of 0.1 C at 25 °C, rested for 10 min, and then discharged to 2.8 V (vs. Li + / Li) at a current density of 0.1 C, cycled for 5 times, and the obtained capacity was recorded as the specific discharge capacity at a rate of 0.1 C.

[0229] Table 1

[0230] Figure 1 shows the X-ray diffraction pattern (XRD) of the halide solid-state electrolyte material prepared in Example 1, and there are no sharp diffraction peaks in the XRD pattern. Figure 2 shows the X-ray diffraction pattern (XRD) of the halide solid-state electrolyte material prepared in Comparative Example 2, and there are obvious diffraction peaks in the XRD pattern. As can be seen from Figures 1 and 2, the halide solid-state electrolyte material LiM 1 x M 2 y X6is amorphous, and the halide solid-state electrolyte material Li 1.6 Ta 0.4 Zr 0.6 Cl 5.9 F 0.1 is crystalline.

[0231] As can also be seen from the test results in Table 1, the amorphous halide solid-state electrolyte material LiM 1 x M 2 y X6has a higher ionic conductivity.

[0232] Table 2

[0233] Table 3

[0234] As can be seen from the test results in Tables 2 and 3, the amorphous halide solid-state electrolyte material LiM 1 x M 2 y X6can improve the stability of the halide solid-state electrolyte material to sulfide solid-state electrolyte materials while retaining the high ionic conductivity of LiTaCl6, and can make the solid-state battery cell have high first-cycle coulombic efficiency, good cycle stability, and good rate performance.

[0235] It should be noted that the present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and embodiments having substantially the same configuration and playing the same role and effect within the scope of the technical solutions of the present disclosure are all included in the technical scope of the present disclosure. Furthermore, other modes obtained by applying various modifications to the embodiments that can be thought of by those skilled in the art, or by combining part of the configuration elements of the embodiments, without departing from the spirit of the present disclosure, are also included in the scope of the present disclosure.

Claims

1. A positive electrode sheet, wherein, The positive electrode sheet includes a positive electrode active material and a halide solid electrolyte material, the halide solid electrolyte material is amorphous, the molecular formula of the halide solid electrolyte material is LiM 1 x M 2 y X6, M 1 Including one or both of Ta, Nb, M 2 Including one or more of trivalent metal elements, tetravalent metal elements, X including one or more of halogen elements, 0.5≤x<1, and LiM 1 x M 2 y X6is electrically neutral.

2. The positive electrode sheet according to claim 1, wherein The halide solid-state electrolyte material coats at least part of the surface of the positive electrode active material.

3. The positive electrode sheet according to any one of claims 1-2, wherein 0.6≤x≤0.9。 4. The positive electrode sheet according to any one of claims 1-3, wherein, M 1 including Ta; and / or, M 2 one or more elements selected from the group consisting of Bi, Sb, As, Sc, Y, La, Pr, Nd, Eu, Gd, Tb, Ho, Er, Tm, Yb, Lu, Zr, Hf, Ce, Ge; and / or, X comprises one or more of Cl, Br, F.

5. The positive electrode sheet according to any one of claims 1-4, wherein, M 2 one or more elements including Y, Zr, Hf; and / or, X comprises Cl, or X comprises Cl and F, or X comprises Cl and Br, or X comprises Cl, Br and F.

6. The positive electrode sheet according to any one of claims 1-5, wherein, The molecular formula of the halide solid-state electrolyte material is LiM 1 x M 2 y Cl 6-z F z 0.1≤z≤0.5; Alternatively, the halide solid-state electrolyte material has a molecular formula of LiM 1 x M 2 y Cl 6-p-z Br p F z 0.1≤p≤3, 0.1≤z≤0.

5.

7. The positive electrode sheet according to any one of claims 1 to 6, wherein The mass ratio of the positive electrode active material to the halide solid-state electrolyte material is 99:1 to 60:

40.

8. The positive electrode sheet according to any one of claims 1-7, wherein, The halide solid-state electrolyte material has a volume distribution particle size Dv90 of 0.5 pm to 3 pm; and / or, The positive electrode active material has a volume distribution particle size Dv50 of 3 pm to 5 pm.

9. The positive electrode sheet according to any one of claims 1 to 8, wherein The halide solid-state electrolyte material has an ionic conductivity of 2 mS / cm to 7 mS / cm at 25 °C.

10. The positive electrode sheet according to any one of claims 1-9, wherein, The positive electrode active material comprises one or more of lithium transition metal oxides and modified materials thereof, lithium-containing phosphates and modified materials thereof, lithium titanate, sulfur, selenium, tellurium; and / or, The positive electrode sheet further comprises a positive electrode conductive agent and / or a positive electrode binder.

11. The positive electrode sheet according to any one of claims 1 to 10, wherein The positive electrode sheet further comprises a positive electrode current collector, and the positive electrode active material and the solid-state electrolyte material are located on at least one surface of the positive electrode current collector.

12. A solid-state battery cell comprising a negative electrode sheet, an electrolyte sheet, and the positive electrode sheet according to any one of claims 1-11, wherein the electrolyte sheet is located between the negative electrode sheet and the positive electrode sheet.

13. The solid-state battery cell according to claim 12, wherein, The negative electrode sheet comprises one or more of graphite, graphene, carbon nanotubes, mesocarbon microbeads, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, metal oxides, lithium, lithium alloys, lithium composite materials; and / or, The electrolyte sheet comprises a sulfide solid-state electrolyte material.

14. A battery device comprising a plurality of solid-state battery cells according to any one of claims 12-13.

15. An electrical device comprising the solid-state battery cell according to any one of claims 12-13 or the battery device according to claim 14.

16. A halide solid state electrolyte material, wherein, The halide solid electrolyte material is amorphous, the molecular formula of the halide solid electrolyte material is LiM 1 x M 2 y X6, M 1 Including one or both of Ta, Nb elements, M 2 Including one or more of trivalent metal elements, tetravalent metal elements, X including one or more of halogen elements, 0.5≤x<1, and LiM 1 x M 2 y X6is electrically neutral.

17. A method of making a halide solid state electrolyte material comprising the steps of: In an inert atmosphere, halides of M 1 , halides of M 2 , halides of Li are ball-milled in stoichiometric ratio to obtain amorphous LiM 1 x M 2 y X6, M 1 comprises one or both of Ta and Nb, M 2 comprises one or more of trivalent metal elements and tetravalent metal elements, X comprises one or more of halogen elements, 0.5≤x<1, and LiM 1 x M 2 y X6is electrically neutral.

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