Cathode materials and methods of formation

Abstract

A cathode material can include a substrate comprising an active cathode material and a coating covering at least a portion of the substrate. The coating material can include CF X and M2CO3, where M can include an alkali metal. In one embodiment, the coating can include MF. In another embodiment, M can include Li.

Description

Technical Field

[0001] The following section discusses cathode materials and their formation methods. Background Technology

[0002] Compared to conventional lithium-ion batteries, solid-state lithium batteries are expected to offer higher energy density and faster recharge times, while causing fewer safety issues. Current solid electrolyte materials include oxide, halide, sulfide, fluoride, and solid polymer electrolytes. The stability of the electrolyte material plays a role in the performance of solid-state lithium batteries. There is an ongoing industrial need for improved solid electrolyte and electrode materials. Attached Figure Description

[0003] This disclosure will be better understood by referring to the accompanying drawings, and many features and advantages of this disclosure will become apparent to those skilled in the art.

[0004] Figure 1A and Figure 1B Including illustrations of the cathode material according to the implementation scheme.

[0005] Figure 2 This includes a cross-sectional view of a cathode material according to one embodiment.

[0006] Figure 3 Includes a cross-sectional view of a multi-layered structure according to one implementation scheme.

[0007] Figure 4 Includes a diagram of a method according to one implementation scheme.

[0008] Figure 5A This includes a curve showing the differential capacity of the sample versus voltage.

[0009] Figure 5B A diagram showing the crystal structure of the cathode material.

[0010] Figure 5C This includes a graph of the differential capacity versus voltage for a sample according to one embodiment.

[0011] Figure 5D and Figure 6A Includes a graph of the sample's specific capacity versus the number of cycles.

[0012] Figure 6B Including -Z of samples according to the implementation plan lmag For Z re The curve graph.

[0013] Figure 6C Including Z of the sample according to the implementation plan re For ω -1 / 2 The curve graph.

[0014] Figure 7 Includes a graph of the sample's specific capacity versus the number of cycles.

[0015] Figure 8 Includes a graph of the sample's specific capacity versus voltage.

[0016] Those skilled in the art should understand that the elements in the accompanying drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some elements in the drawings may be enlarged relative to other elements to aid in understanding embodiments of the invention. The same reference numerals are used in different drawings to indicate similar or identical items. Detailed Implementation

[0017] The following description, taken in conjunction with the accompanying drawings, is provided to aid in understanding the teachings disclosed herein. The following discussion will focus on specific implementations and methods of carrying out the teachings. This focus is provided to aid in describing the teachings and should not be construed as a limitation on the scope or applicability of the teachings.

[0018] As used herein, the terms “comprising,” “including,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of features is not necessarily limited to those features, but may include other features not expressly listed or inherent to such a process, method, article, or apparatus. Furthermore, unless expressly stated to the contrary, “or” indicates inclusion, not exclusivity. For example, condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0019] The terms "an" or "a" are used to describe the elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. The description should be understood to include one or at least one, and the singular includes the plural, or vice versa, unless it is clearly indicated otherwise.

[0020] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Materials, methods, and examples are exemplary only and are not intended to be limiting.

[0021] Embodiments herein relate to a cathode material comprising a substrate and a coating material covering at least a portion of the substrate, wherein the substrate may contain a cathode active material. In one embodiment, the substrate may contain particles containing the cathode active material. The cathode material may be a suitable component of a non-aqueous battery, such as a solid-state battery, including solid-state lithium batteries, solid-state sodium batteries, etc., or any combination thereof. In an exemplary embodiment, the cathode material may be in direct contact with a solid electrolyte material, such as a solid halide-based electrolyte material or another solid electrolyte material. The cathode material may have improved ion diffusion rates, capacity retention, reversible phase transitions, or any combination thereof. The cathode material may also contribute to improved stability of the solid electrolyte material and improved performance of the solid-state battery.

[0022] Another embodiment relates to a method for forming a cathode material. This method allows for improved formation of the cathode material and facilitates the formation of cathode materials with improved properties.

[0023] In one embodiment, the cathode material may include a coating material comprising fluorinated carbon (also referred to herein as "CF2C ... x M(t) and M2CO3, wherein M comprises an alkali metal. In one aspect, M may comprise Li, Na, Cs, Rb, or combinations thereof. In one example, M may comprise Li. In another example, M may comprise Na. In yet another example, M may comprise Li and another alkali metal, such as Na, Cs, or both. In a specific example, M may consist essentially of at least one of Li and Na.

[0024] In one embodiment, the coating material may comprise MF. In one aspect, MF may comprise LiF, NaF, CsF, RbF, or combinations thereof. In one example, MF may comprise LiF. In another example, MF may comprise NaF. In yet another example, MF may comprise LiF and another alkali metal fluoride, such as NaF, CsF, or both. In a specific example, MF may consist substantially of at least one of LiF and NaF.

[0025] In one embodiment, the coating may comprise fluorinated carbon, comprising stoichiometric amounts of monofluorinated carbon, substoichiometric amounts of monofluorinated carbon, or any combination thereof. In one aspect, the fluorinated carbon may comprise CF1, C2F4, CF2, CF3, CF4, or any combination thereof. In a specific aspect, the coating may comprise CF4, CF2, or both. In another aspect, the coating may have a specific ratio between the fluorinated carbon components. XPS can be used to detect the fluorinated carbon components. In yet another specific aspect, the coating may comprise CF1.

[0026] In one embodiment, the cathode material may include a coating of a specific average thickness, which may contribute to improved performance and / or properties of the cathode material. In one aspect, the coating may have an average thickness of less than one micrometer. For example, the coating may have an average thickness of up to 100 nm, such as up to 80 nm, up to 70 nm, up to 60 nm, up to 50 nm, up to 40 nm, up to 30 nm, or up to 20 nm. In another example, the coating may have an average thickness of at least 1 nm, such as at least 2 nm, at least 5 nm, at least 7 nm, at least 10 nm, at least 13 nm, at least 15 nm, at least 18 nm, or at least 20 nm. Furthermore, the coating may have an average thickness within a range including any of the minimum and maximum values ​​described herein.

[0027] As used in this paper, the average thickness of the coating can be determined by using transmission electron microscopy to analyze cathode material samples with sample sizes that are statistically representative of the cathode material.

[0028] In one embodiment, the coating may cover at least a portion of the substrate. On one hand, the coating may extend continuously along at least a portion of the substrate. On the other hand, the coating may have a specific coverage percentage over the substrate, which may benefit the improved performance and / or properties of the cathode material. For example, the coating may cover at least 20%, at least 30%, at least 40%, at least 50%, or most of the substrate. In another example, the coating may substantially cover the entire substrate. In yet another example, the coating may cover no more than 99%, no more than 96%, no more than 90%, no more than 88%, no more than 85%, or no more than 80% of the substrate. Furthermore, in a specific example, the coating may have a coverage percentage within a range including either the minimum or maximum percentage described herein.

[0029] In one embodiment, the cathode material may be in powder form. In another embodiment, the cathode material may be in suspension form. In yet another embodiment, the cathode material may comprise a substrate in particulate form. In one aspect, the substrate may comprise a plurality of particles containing cathode active material. In another aspect, at least a portion of the particles may have a coating. For example, at least 20% by weight, at least 30% by weight, at least 40% by weight, or at least 50% by weight of the total weight of the particles may include a coating. In a specific aspect, at least a majority of the total weight of the particles, such as greater than 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, or at least 95% by weight, may include a coating. In a specific example, substantially all of the particles, such as at least 95% by weight or at least 98% by weight of the total weight of the particles, may include a coating. More specifically, all of the particles, such as 100% by weight of the particles, may include a coating. In another aspect, not all of the particles may include a coating. For example, no more than 99% by weight of particles may include a coating, such as no more than 98% by weight, no more than 96% by weight, no more than 94% by weight, no more than 92% by weight, no more than 90% by weight, or no more than 88% by weight of particles. Furthermore, the cathode material may contain a certain amount of coated particles, wherein this amount may be within either the minimum percentage or the maximum percentage described herein.

[0030] In another embodiment, the cathode material may include at least 20% of the total number of coated particles, such as at least 30%, at least 40%, or at least 50% of the total number of particles. In one specific embodiment, at least a majority of the total number of particles, such as greater than 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95%, may include a coating. In one specific example, substantially all of the particles, such as at least 95% or at least 98% of the total number of particles, may include a coating. More specifically, all particles may include a coating. In another embodiment, not all particles may include a coating. For example, no more than 99% of the particles may include a coating, such as no more than 98%, no more than 96%, no more than 94%, no more than 92%, no more than 90%, or no more than 88% of the total weight of the particles may include a coating. Furthermore, the cathode material may contain a certain amount of coated particles, wherein this amount may be within the range of either the minimum percentage or the maximum percentage described herein. As disclosed herein, at least 200 randomly selected different particles were analyzed to determine the number of particles with coatings.

[0031] In one embodiment, the content of coated particles can be determined using energy-dispersive X-ray analysis (EDX). A cathode material sample with a statistically representative sample size of the cathode material can be analyzed by EDX. The number or weight of coated particles can be determined based on the EDX results, and the percentage of coated particles relative to the total number or weight of the analyzed particles can be used as the content of coated particles in that batch of cathode material.

[0032] See Figure 1A An exemplary cathode material 100 is illustrated. The cathode material 100 may comprise a plurality of particles, each particle including a substrate in the form of particles 108 and a coating 106 covering the particles 108. The coating 106 may be in direct contact with the particles 108. In the illustrated example, the cathode material may comprise particles 102 including a coating 106 that substantially completely covers the particles 108. The particles 102 may have a substantially uniform coating thickness. In another embodiment, the cathode material may comprise particles with varying coating thicknesses. For example, the coating thickness may decrease and / or increase along the surface of the coated particles.

[0033] In some cases, cathode material 100 may comprise coated particles 103, wherein coating 106 may substantially completely cover particles 108 and may vary in coating thickness.

[0034] In some cases, the cathode material 100 may comprise coated particles 104, a portion of which may be covered by a coating 106. Figure 1A In the illustrated embodiment, particles 104 may have a coating thickness variation along the surface of particles 108. In another embodiment, partially coated particles and / or fully coated particles may have a substantially uniform coating thickness.

[0035] In another embodiment, the cathode material may comprise coated particles, wherein at least some of the particles may have a substantially uniform coating thickness along the coated surface. For example, at least 20% of the total number of coated particles may have a substantially uniform coating thickness, such as at least 30%, at least 40%, or at least 50% of the particles may have a substantially uniform coating thickness. In a specific example, a majority of the coated particles may include a coating with a substantially uniform thickness, such as at least 55%, at least 60%, at least 70%, at least 80%, or at least 90% of the coated particles may include a coating with a substantially uniform thickness. In a specific example, substantially all of the coated particles may include a coating with a substantially uniform thickness. In another example, no more than 98%, no more than 95%, no more than 92%, no more than 90%, or no more than 88% of the coated particles may include a substantially uniform coating thickness.

[0036] In another case, the cathode material 100 may comprise uncoated particles 109. As shown, the cathode material 100 may comprise a majority of particles including a coating 106.

[0037] In another embodiment, the cathode material 100 may include up to 50% by weight of uncoated particles, such as less than 50% by weight, no more than 40% by weight, no more than 30% by weight, no more than 20% by weight, no more than 10% by weight, no more than 5% by weight, no more than 3% by weight, or no more than 1% by weight of uncoated particles. The content of uncoated particles can be determined using EDX in a manner similar to that described with respect to determining the content of particles including a coating.

[0038] In yet another embodiment, the cathode material 100 may contain up to 50% of the total number of uncoated particles, such as less than 50%, no more than 40%, no more than 30%, no more than 20%, no more than 10%, no more than 5%, no more than 3%, or no more than 1% of the total number of uncoated particles. In one specific embodiment, the cathode material may be substantially free of uncoated particles.

[0039] In one embodiment, the cathode material may comprise particles having an average particle size. In one example, the average particle size may be submicron to hundreds of micrometers or even larger. In another example, the average particle size may be 1 micrometer to 500 micrometers. In yet another example, the average particle size may be 1 micrometer to 10 micrometers, such as 2 micrometers to 5 micrometers. In yet another example, the cathode material may comprise loose particles, agglomerated particles, aggregates, or any combination thereof. Those skilled in the art will understand that the cathode material may have an average particle size suitable for the application of the cathode material.

[0040] In one embodiment, the cathode material may be in the form of a sheet, strip, block, film, or any other shape or combination thereof. See also Figure 1B The diagram illustrates a cross-sectional view of an exemplary cathode material 110 according to one embodiment. The cathode material 110 may include a body 111 containing a plurality of particles 112. The body 110 may have a length L and a thickness t. In one embodiment, the particles 112 may include particles relative to... Figure 1A Any or all of the features described for the illustrated particles 102, 103, 109, and 104. It should be understood that cathode material 110 may include any or all of the features described with respect to cathode material 100, except that cathode materials 110 and 100 may be in different forms.

[0041] In one embodiment, the cathode material may comprise a plurality of particles, wherein at least some of the particles may have a coating coverage of at least 50% of the particle's surface area. For example, at least 30% of the total number of particles, such as at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95%, may have a coating coverage of at least 50% of the particle's surface area. In another example, all or substantially all of the particles may have a coating coverage of at least 50% of the particle's surface area. In yet another example, no more than 95% of the total number of particles, such as no more than 90%, no more than 80%, or no more than 70%, may have a coating coverage of at least 50% of the particle's surface area. Furthermore, the cathode material may comprise a certain amount of particles having a coating coverage of at least 50%, wherein this amount may be within the range of either the minimum percentage or the maximum percentage described herein.

[0042] In another embodiment, the cathode material 100 may have a specific average coating coverage that may contribute to improved properties and / or performance of the cathode material. The average coating coverage may be determined based on analysis of a cathode material sample having a sample size that is statistically representative of the cathode material. Transmission electron microscopy may be used to determine the coating coverage of each particle on the particle surface area. The average coating coverage may be the sum of the coating coverage of all analyzed particles divided by the number of particles. In one aspect, the cathode material may have an average coating coverage of at least 30%, such as at least 40%, at least 50%, at least 60%, at least 70%, at least 75%, at least 80%, at least 90%, or at least 95%. In a specific example, the cathode material may have an average coating coverage of 100%. In another aspect, the cathode material may have an average coating coverage of no more than 99%, no more than 96%, no more than 93%, no more than 90%, no more than 88%, no more than 85%, or no more than 80%. Furthermore, the cathode material may include an average coating coverage within a range including either the minimum percentage or the maximum percentage described herein.

[0043] In one embodiment, the cathode material may comprise a substrate in the form of a strip, sheet, block, film, or any combination thereof. The substrate may contain the active cathode material. See also Figure 2 The diagram illustrates a cross-sectional view of an exemplary cathode material 120, which includes a substrate 126 containing an active cathode material and a coating 124 covering the substrate 126. The substrate may have a length L and a thickness t.

[0044] The substrate 126 may include a main surface 127 and another main surface 128 opposite to the main surface 127. A coating 124 may cover at least one of the main surfaces 127 or 128, such as the main surface 127 as shown in the figure. Those skilled in the art will understand that the coating 124 may cover the main surface 128. In at least one embodiment, the cathode material 120 may include a coating 124 covering both the main surfaces 127 and 128 of the substrate 126.

[0045] In another embodiment, the cathode material 120 may include a coating 124 that covers at least a portion of the substrate 126. In another embodiment, the coating 124 may cover at least a portion of the main surfaces 127 and / or 128 of the substrate 126. In another embodiment, the coating 124 may have a specific coverage on the substrate 126 that may contribute to improved performance and / or properties of the cathode material. For example, the coating 124 may cover at least 20% of the main surface of the substrate, such as at least 30%, at least 40%, at least 50%, or most of the main surface of the substrate. In another example, the coating may substantially cover the entire main surface of the substrate. In another example, the coating may cover no more than 99%, no more than 96%, no more than 90%, no more than 88%, no more than 85%, or no more than 80% of the main surface of the substrate. Furthermore, in a specific example, the coating 124 may have a coverage within a range including either the minimum or maximum percentage described herein.

[0046] In one embodiment, the substrate may include a coating in the form of a thin film. In another embodiment, the cathode material may include a relatively dense coating. In one aspect, the coating may have a density of at least 90% of the theoretical density, such as at least 93%, at least 95%, at least 98%, or even at least 99% of the theoretical density. Specifically, the coating may have a density greater than that formed when the coating is formed by a densification process involving calcination. In another aspect, the coating may have a relatively low porosity. Porosity may consist of voids that may be present in the coating. For example, the coating may include a minimum amount of pores within the coating. Porosity may differ from the uncoated areas of the particle surface. For example, the cathode material may contain particles that can be partially covered by the coating, wherein the coating may include a minimum amount of pores. In one specific aspect, the cathode material may include a coating having a porosity of no more than 7% by volume, such as no more than 5% by volume, no more than 3% by volume, or no more than 1% by volume. In one specific example, the coating may be substantially pore-free. In another example, the cathode material may include a coating having a porosity of at least 0.1% by volume of the total volume of the coating, such as at least 0.4% by volume, at least 0.7% by volume, at least 1% by volume, or at least 2% by volume. Furthermore, the cathode material may include a coating having a porosity within the range of either the minimum or maximum percentages described herein.

[0047] In one embodiment, the cathode material may include a coating that can have a relatively smooth surface. In one aspect, the coating may have a relatively low surface roughness. For example, the surface roughness of the coating may be lower than that of a coating formed by a densification process involving calcination. Surface roughness can be determined by analyzing a cathode material sample having a sample size that is statistically representative of the cathode material using scanning electron microscopy, transmission electron microscopy, or both.

[0048] In one embodiment, the cathode material may include a coating having a substantially uniform thickness. In another embodiment, the coating may have a thickness variation along the coated area of ​​the substrate. In a specific embodiment, the coating may have a particular average thickness variation along the coated surface, which may contribute to improved properties and / or performance of the cathode material. In one example, the average thickness variation may be within ±50% of the average coating thickness, such as within ±40%, ±30%, ±20%, ±10%, or ±5% of the average coating thickness.

[0049] In one embodiment, the cathode material may include a coating containing specific amounts of M2CO3 and CF. x And / or MF, which can contribute to improved properties and / or performance of the cathode material. In another embodiment, the coating may contain specific relative amounts of M2CO3, CF xAnd / or MF, which may contribute to improved properties and / or performance of the cathode material. Relative content can be determined by X-ray photoelectron spectroscopy (XPS) analysis. Those skilled in the art will understand that relative content is compared to the content of a particular element. In this disclosure, M2CO3, CF... x The relative content of MF is compared to the Ni content determined by XPS as follows. Full measurement spectra of all existing elements on the surface of the coated active cathode material are obtained. The peak area associated with each peak in the measurement spectrum is then extracted. The extracted peak areas are corrected by taking into account the sensitivity factor for each element (i.e., dividing the peak intensity by the element's sensitivity factor), and all peak areas are normalized relative to Ni.

[0050] In one specific implementation, the relative content of M2CO3 may be at least 0.4, at least 0.6, at least 0.7, at least 0.8, at least 0.9, or at least 1.0. Alternatively, the relative content of M2CO3 may not exceed 1.5, 1.3, 1.1, 0.9, or 0.8. Furthermore, the relative content of M2CO3 may be within a range including any of the minimum and maximum values ​​described herein.

[0051] In one embodiment, the coating may contain at least 0.05, such as at least 0.07, at least 0.09, at least 0.11, or at least 0.13, of CF. x The relative content. Alternatively, CF x The relative content may be no greater than 0.42, 0.40, 0.38, 0.35, 0.32, 0.30, 0.28, 0.27, 0.25, 0.23, 0.21, 0.18, 0.15, or 0.13. In addition, CF... x The relative content can be within the range of either the minimum or maximum value described herein.

[0052] In one embodiment, the coating may contain a relative content of MF of at least 1.2, at least 1.4, at least 1.7, at least 1.9, at least 2.1, at least 2.3, at least 2.5, at least 2.7, at least 2.9, at least 3.0, or at least 3.2. Alternatively or additionally, the relative content of MF may not exceed 6.4, 6.1, 5.8, 5.5, 5.2, 4.9, 4.6, 4.2, 3.9, 3.7, 3.5, 3.1, or 3.0. Furthermore, the relative content of MF may be within a range including either the minimum or maximum values ​​described herein.

[0053] In one embodiment, the coating may have a relative content of M2CO3 and CF. x A specific content ratio C1 of the relative content can be beneficial to the improved properties and / or performance of the cathode material. In another embodiment, the ratio C1 can be at least 3.6, at least 3.8, at least 4.1, at least 4.5, at least 4.8, at least 5.1, at least 5.3, at least 5.7, at least 5.9, at least 6.3, at least 6.7, at least 6.9, at least 7.2, at least 7.5, at least 7.8, at least 8.1, at least 8.3, at least 8.5, or at least 8.7. Alternatively or additionally, the ratio C1 can be no greater than 11.5, no greater than 11.2, no greater than 10.8, no greater than 10.5, no greater than 10.1, no greater than 9.7, no greater than 9.4, no greater than 9.1, no greater than 8.8, no greater than 8.6, or no greater than 8.3. Furthermore, the ratio C1 can be within a range including either the minimum or maximum value described herein.

[0054] In one embodiment, the coating may have a specific content ratio C2 of the relative content of MF to the relative content of M2CO3, which may be beneficial to the improved properties and / or performance of the cathode material. In another embodiment, the ratio C2 may be at least 1.2, at least 1.4, at least 1.6, at least 1.8, at least 2.1, at least 2.3, at least 2.5, at least 2.7, at least 2.9, at least 3.0, or at least 3.2. Alternatively or additionally, the ratio C2 may not exceed 6.4, 6.1, 5.8, 5.5, 5.2, 4.9, 4.6, 4.3, 4.1, 3.8, 3.5, 3.2, 3.1, or 2.9. Furthermore, the ratio C2 may be within a range including either the minimum or maximum value described herein.

[0055] In one embodiment, the coating may have a relative content of MF and CF. xA specific content ratio C3 of the relative content can be beneficial to the improved properties and / or performance of the cathode material. In another embodiment, the ratio C3 may not exceed 35.4, 34.1, 32.8, 31.5, 30.2, 28.9, 28.6, 27.3, 26.1, 25.8, or 24.5. Alternatively or additionally, the ratio C3 may be at least 6.3, 7.8, 9.2, 10.5, 11.1, 12.3, 14.5, 15.2, 16.9, 18.0, 19.5, 21.5, 23.8, 24.5, 25.8, or 26.2. Furthermore, the ratio C3 may be within a range including either the minimum or maximum value described herein.

[0056] In one embodiment, the cathode material may have a specific fluoride concentration, which may contribute to improved properties and / or performance of the cathode material. In another embodiment, the coating may comprise organic fluorides (such as fluorocarbons) and inorganic fluorides (such as MF). In yet another embodiment, the cathode material may have a specific total concentration (C0) of organic and inorganic fluorides. TF This can improve the properties and / or performance of cathode materials. For example, total concentration (C TF The total concentration (C) can be greater than 0, such as at least 5 μg / g, at least 20 μg / g, at least 50 μg / g, at least 90 μg / g, at least 110 μg / g, at least 150 μg / g, at least 205 μg / g, at least 235 μg / g, or greater than 235 μg / g. In a specific example, the total concentration (C) TF The concentration can be at least 236 μg / g, at least 240 μg / g, at least 260 μg / g, at least 290 μg / g, at least 310 μg / g, at least 335 μg / g, at least 355 μg / g, at least 370 μg / g, or at least 390 μg / g. In another example, the total concentration (C) TF The concentration can be less than 805 μg / g, such as up to 800 μg / g, up to 785 μg / g, up to 770 μg / g, up to 730 μg / g, up to 695 μg / g, up to 650 μg / g, up to 601 μg / g, up to 570 μg / g, up to 515 μg / g, up to 475 μg / g, up to 435 μg / g, or up to 395 μg / g. Furthermore, the total concentration can be within the range of either the minimum or maximum values ​​described herein.

[0057] In another embodiment, the cathode material may have a specific organic fluoride (C) OFThe concentration of fluorinated compounds (C) can be beneficial to improving the properties and / or performance of cathode materials. For example, organic fluorides (C) OF The concentration of ) can be at least 0.5 μg / g, such as at least 1 μg / g, at least 2 μg / g, at least 4 μg / g, at least 6 μg / g, at least 8 μg / g, at least 10 μg / g, at least 12 μg / g, or at least 14.5 μg / g. In another example, organofluorine compounds (C OF The concentration of ) can be less than 32.7 μg / g, such as up to 32 μg / g, up to 30 μg / g, up to 27 μg / g, up to 25 μg / g, up to 21 μg / g, up to 19 μg / g, up to 17 μg / g, up to 16 μg / g, up to 15 μg / g, or up to 14.5 μg / g. Furthermore, organofluorine compounds (C...) OF The concentration of ) can be within the range of either the minimum or the maximum value described herein.

[0058] In another embodiment, the cathode material may have a specific inorganic fluoride (C IF The concentration of fluoride can be beneficial to improving the properties and / or performance of cathode materials. For example, inorganic fluorides (C...) IF The concentration of ) can be greater than 0, such as at least 25 μg / g, at least 40 μg / g, at least 75 μg / g, at least 90 μg / g, at least 125 μg / g, or at least 156.5 μg / g, or at least 202.3 μg / g. In a specific example, inorganic fluoride (C IF The concentration of ) can be greater than 202.3 μg / g, such as at least 205 μg / g, at least 210 μg / g, at least 240 μg / g, at least 280 μg / g, at least 310 μg / g, at least 335 μg / g, at least 355 μg / g, at least 370 μg / g, or at least 377.5 μg / g. In another example, inorganic fluoride (C IF The concentration of ) can be less than 770.8 μg / g, such as up to 769 μg / g, up to 750 μg / g, up to 740 μg / g, up to 725 μg / g, up to 680 μg / g, up to 640 μg / g, up to 615 μg / g, up to 605 μg / g, up to 581 μg / g, up to 540 μg / g, up to 515 μg / g, up to 475 μg / g, up to 435 μg / g, up to 395 μg / g, up to 385 μg / g, or up to 378 μg / g. Furthermore, inorganic fluorides (C IF The concentration of ) can be within the range of either the minimum or the maximum value described herein.

[0059] In another embodiment, the cathode material may have a concentration of inorganic fluoride (C IF) and the concentration of the organic fluoride (C OF ) at a specific concentration ratio (C I / O ). In one example, the concentration ratio (C I / O ) can be greater than 22.5, such as at least 23, at least 24, at least 25, or at least 26. In another example, the concentration ratio (C I / O ) can be at most 81, at most 75, at most 70, at most 65, at most 61, at most 56, at most 52, at most 48, at most 43, at most 39, at most 34, at most 31, at most 28, or at most 26. Furthermore, the concentration ratio (C I / O ) can be within a range including any of the minimum and maximum values described herein.

[0060] In one embodiment, the substrate may comprise an active cathode material, and the active cathode material comprises an oxide. Exemplary oxides may comprise one or more metal elements selected from alkali metals, 3d metals, 4d metals, 5d metals, rare earth metals and alkaline earth metals. In another example, the oxide may comprise an alkali metal transition metal oxide. In a specific example, the alkali metal may include Li, Na, or a combination thereof. In another specific example, the oxide may comprise at least one 3d metal, such as Ni. In a specific embodiment, the active cathode material may comprise a lithium-doped nickel oxide material. In one example, the lithium-doped nickel oxide material may comprise an additional dopant. In a more specific embodiment, the active cathode material may comprise Li-Ni-Mn-Co oxide. A specific example may include LiNi x Mn y Co z O2, wherein x>0, y≥0, z≥0, x+y+z=1, and y+z>0. In more specific examples, 0.3<x<0.8, 0.2<y<0.3, 0.1<z<0.4. An even more specific example may include LiNi 0.6 Mn 0.2 Co 0.2 O2.

[0061] See Figure 3 , which illustrates a multilayer structure 300 of one embodiment, comprising a layer 304 covering an electrolyte layer 306 and a third layer 302 opposite the layer 304 across the electrolyte layer 306. The layer 304 may comprise the cathode material described in the embodiments herein. For example, the layer 304 may comprise Figure 1A the cathode material 100 exemplified in or Figure 1B the cathode material 110 exemplified in . In another case, the layer 304 may comprise Figure 2 the cathode material 120 exemplified in . The electrolyte layer 306 may comprise a solid electrolyte material.

[0062] Layer 304 may have a thickness t extending in the stacking direction or y-axis of the multilayer structure 300, a length L extending in the x-axis, and a width extending in the z-axis. It is understood that the thickness, width, and length of other components (such as layers 306 and 302) may extend into layer 304 in the same direction, respectively.

[0063] In one embodiment, layer 304 may be a cathode layer. In one aspect, cathode layer 304 may comprise a cathode material and optional additives. Exemplary additives may include binder materials (such as organic binders), pore-forming agents, fillers (such as conductive fillers (e.g., conductive carbon)), or any combination thereof. In another embodiment, layer 304 may be a composite layer comprising a cathode material and an ion-conducting material. For example, layer 304 may comprise the solid electrolyte material described in the embodiments herein. In another embodiment, layer 304 may comprise multiple layers. In one specific embodiment, a coating of cathode material may be in direct contact with electrolyte layer 306.

[0064] In one embodiment, the electrolyte layer may comprise a solid electrolyte material, including halide-based electrolyte materials, sulfide-based electrolyte materials, oxide-based electrolyte materials, hydroxy halides, halide oxides, organic electrolyte materials such as polymer electrolytes, or any combination thereof.

[0065] In one specific implementation, the cathode material may be particularly suitable for use with solid electrolyte materials that may be easily degraded, such as sulfide electrolyte materials, halide electrolyte materials, or any combination thereof.

[0066] In one specific embodiment, the electrolyte layer may comprise a halide-based electrolyte material. In one aspect, the halide-based electrolyte material may comprise anions, including halogens selected from the group consisting of F, Cl, Br, and I. In another specific aspect, the halide-based electrolyte material may comprise at least two halide anions. More specific examples of the halide-based electrolyte material may include at least two halide anions selected from the group consisting of F, Cl, and Br.

[0067] In another embodiment, the halide-based electrolyte material can be made from M 3-z (Me k+ ) f X 3-z+k* f represents the following: -3≤z<3; 2≤k≤6; 0≤f≤1; M may contain alkali metals; and X may contain halogens. Me may contain divalent, trivalent, tetravalent, pentavalent, hexavalent metals, or any combination thereof.

[0068] In one specific implementation scheme, the halide-based electrolyte material can be made from Li 3-x-f M f RE 1-y Me k y (Cl 1-u-p- q Br u F p I q ) 6-x+y*(k-3) This indicates that -1 <= x <= 1; 0 <= y <= 1; 0 <= u < 1; 0 <= p <= 1 / 3; 0 <= q <= 1 / 6; 0 < (u + p + q) < 1; 0 <= f <= 0.3. In a more specific embodiment, the halide material may be derived from Li 3-x RE 1-y Me k y (Cl 1- u Br u ) 6-x+y*(k-3) This indicates that 0.08 <= u <= 0.67. M can be at least one alkali metal element other than Li. RE can be a rare earth element. Me is at least one element selected from the group consisting of group IIIB elements, group IVB elements, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Al, Sn, Pb, Bi, Sb, Mg, Ca, Ga, and Ge, where Me is different from RE; and k can be the valence of Me.

[0069] In another embodiment, the halide electrolyte material may be made of Li a M a Me b Me' b’ X c X' c’ This indicates that a halogen can be represented by X and X', and that a specific crystallographic phase transition can occur, where X and X' can represent different halogens, and Me' can represent another Me. In one respect, the crystallographic phase transition can occur at (b / (b+b')). t *0.84 t *Within the stoichiometric range of 1.16, where (b / (b+b')) t This corresponds to a crystallographic phase transition on a crystallographic phase diagram at temperatures between 20°C and 25°C. Alternatively, the crystallographic phase transition can occur at (c / (c+c')). t *0.84 <c / (c+c')<(c / (c+c')) t *Within the stoichiometric range of 1.16, where (c / (c+c')) t ​This corresponds to a crystallographic phase transition on a crystallographic phase diagram at temperatures between 20°C and 25°C. In another aspect, the crystallographic phase transition can occur at (a / (a+a')). t *0.84 t *Within the stoichiometric range of 1.16, where (a / (a+a')) t This corresponds to a crystallographic phase transition on a crystallographic phase diagram at a temperature of 20°C to 25°C. In another embodiment, the halide electrolyte material may comprise NH4X, where X can be a halogen of Cl, Br, F, or I, and NH4... + It can replace a portion of alkali metals.

[0070] Specific examples of solid electrolyte materials may include Li 3-a Na a Y(Br x Cl y )6, where 0 ≤ a ≤ 0.33 and x + y = 1. In a more specific example, x ≤ y. Even more specific examples of solid electrolyte materials may include Li3YBr6, Li3YCl6, Li3Y(Cl 0.67 Br 0.33 6. Li3Y(Cl 0.79 Br 0.21 6. Li3Y(Br) 0.35 Cl 0.65 6. Li3Y(Cl 0.8 Br 0.2 6. Li3Y(Cl 0.19 Br 0.81 6. Li3(Y) 0.95 Yb 0.05 )1(Cl 0.83 Br 0.17 6. Li3(Y) 0.95 In 0.05 (Cl) 0.9 Br 0.1 6. Li 2.95 (Y 0.95 Zr 0.05 (Cl) 0.9 Br 0.1 6. Li3(Y) 0.85 In 0.15 Cl6、(Li 0.955 Na 0.045 )3Y1Cl6、Li3Y(Cl 0.41 Br 0.59 6. Li3Y(Cl 0.62 Br 0.38 6. Li3Y(Cl 0.67 Br​0.33 6. Li3Y(Cl 0.79 Br 0.21 6. or any combination thereof.

[0071] In another embodiment, the halide material may contain a relatively low amount of impurity phases, including water-insoluble impurity phases, binary halide phases, ternary halide phases, or any combination thereof. For example, the halide material may have a total content of one or more water-insoluble impurity phases, such as no more than 0.11% by weight, 0.09% by weight, 0.08% by weight, 0.07% by weight, 0.05% by weight, 0.04% by weight, 0.03% by weight, 0.01% by weight, 0.008% by weight, 0.006% by weight, 0.004% by weight, or 0.003% by weight, of the total weight of the halide material. In each case, the majority of the water-insoluble impurity phase may comprise one or more phases of rare earth halide oxides, Me halide oxides, rare earth oxides, Me oxides, or any combination thereof. In another case, the water-insoluble impurity phase may consist essentially of one or more phases of rare earth halide oxides, halide oxides of Me, rare earth oxides, oxides of Me, or any combination thereof.

[0072] In another example, the halide material may have a total content of no more than 10% by weight of the total weight of the halide material, such as no more than 9% by weight, no more than 8% by weight, no more than 7% by weight, no more than 6% by weight, no more than 5% by weight, no more than 3% by weight, no more than 2% by weight, no more than 1% by weight, or no more than 0.5% by weight of the binary halide phase. The binary halide may contain a cation of a metal element selected from the group consisting of Li, M, Me, and RE.

[0073] In another example, the halide material may have a ternary halide phase comprising no more than 6% by weight of the total weight of the halide material, such as no more than 5% by weight, no more than 3% by weight, no more than 2% by weight, no more than 1% by weight, or no more than 0.5% by weight of the total weight of the halide material. An exemplary ternary halide may comprise two metal cations and one halide anion, such as an alkali metal-rare earth metal halide, or one metal element and two halide anions, or both. An exemplary metal cation may comprise cations of Li, M, RE, and / or Me metal elements. In a particular embodiment, the halide material may be substantially free of binary halide phases, ternary halide phases, oxynitride phases, and oxyhalide phases. In a more specific embodiment, the halide material may consist substantially of a single phase.

[0074] In another embodiment, the solid electrolyte material may comprise a single-crystal material or a polycrystalline material. In yet another embodiment, the solid electrolyte material may comprise an oriented polycrystalline halide electrolyte material, wherein the grains of the polycrystalline halide electrolyte material may be oriented in a specific crystallization direction, which can benefit from improved ionic conductivity. For example, the grains may be oriented such that the ionic conductivity in the extension direction of the thickness t of the electrolyte layer 306 can be greater than that in the length L direction, the width direction, or another crystallization direction of the electrolyte layer.

[0075] In one embodiment, the coating of the cathode material can be in direct contact with the solid electrolyte material. For example, Figure 1A and Figure 2 The coatings 106 and 124 illustrated in the examples can be used with... Figure 3 The electrolyte layer 306 is in direct contact.

[0076] See Figure 3 An interface 305 between layers 304 and 306 is illustrated. In one embodiment, at least a portion of interface 305 may be defined by coatings of cathode material and solid electrolyte material. In a specific embodiment, multilayer structure 300 may include interface 305, which includes a specific contact area defined by coatings of cathode material and solid electrolyte material, which may contribute to improved performance and / or characteristics of the multilayer structure. In one aspect, the contact area may be at least 50% of the entire interface 305, such as at least 55%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95% of the entire interface. In a specific embodiment, the entire interface 305 may be defined by coatings and solid electrolyte material. In another aspect, the contact area may be up to 99% of the entire interface 305, such as up to 95%, up to 93%, up to 90%, up to 87%, or up to 85% of the entire interface 305. Furthermore, the contact area defined by coatings and solid electrolyte material may be within the range of either the minimum or maximum percentage described herein.

[0077] In one embodiment, the third layer 302 may be the anolyte, anode, another electrolyte layer, or another component of the solid-state battery, or any combination thereof. Those skilled in the art will understand that the multilayer structure contemplated in this disclosure may not necessarily include three layers, and in some cases, the multilayer structure 200 may include a cathode layer 304 covering the electrolyte layer 306 without the third layer 302 shown in the figure.

[0078] Compared to cathode materials with the same active cathode material but without a coating, the cathode materials described in the embodiments herein possess improved properties. For example, the cathode material may have improved stability, reduced reactivity with the solid electrolyte material, improved reversible phase transition, wettability, processability, lithium-ion diffusion, or any combination thereof. In one specific embodiment, the cathode material may be a suitable component for Li and / or Na solid-state batteries and may contribute to improved performance of the solid-state battery. In a more specific embodiment, the cathode material may be in direct contact with a halide solid electrolyte material and may significantly improve the stability of the solid electrolyte material and the overall performance of the solid-state battery. Such improvements can be reflected in improved charge and recharge capabilities, specific capacity during charge-recharge cycles, reduced degradation of the electrolyte material, or any combination thereof.

[0079] In one embodiment, the cathode material, such as respectively in Figure 1A , Figure 1B or Figure 2 The cathode materials 100, 110, and 120 illustrated herein may include specific σ-(Warburg coefficient), which may contribute to improved properties and performance of the cathode material. In one aspect, the cathode material may include an Ω·s value not exceeding 2940 Ω. -1 Such as not greater than 2800Ωs -1 Not greater than 2500Ωs -1 Not greater than 2200Ωs -1 Not greater than 2000Ωs -1 1800Ωs -1 1600Ωs -1 1490Ωs -1 or not greater than 1350Ωs -1 The σ-(Warburg coefficient). On one hand, the cathode material may include at least 500 Ωs. -1 At least 700Ωs -1 At least 850Ωs -1 At least 1000Ωs -1 At least 1150Ωs -1 At least 1300Ωs -1 or at least 1400Ωs -1 The σ-(Warberg coefficient). Furthermore, the cathode material may include a σ-(Warberg coefficient) within a range including either the minimum or maximum value described herein.

[0080] σ-(Warberg coefficient) can be calculated as follows.

[0081] The battery can be used for testing. The battery may comprise 60% by weight of cathode material and 40% by weight of Li3Y (Cl...). 0.8 Br0.2 )6 and relative to the cathode material and Li3Y(Cl 0.8 Br 0.2 The cathode granules are made of 0.5% by weight of conductive carbon, which serves as the Li foil for the anode, and the electrolyte is Li3Y(Cl). 0.8 Br 0.2 6) pressed granules.

[0082] The diffusion of Li+ at the cathode is calculated using the slope of the line at low frequencies (such as 0.1 Hz to 1 Hz) in the electrochemical impedance spectroscopy and the following equation:

[0083] Z' re =R e +R ct +σ w ω -1 / 2

[0084] Dion = R 2 T 2 / 2n 4 F 4 A 2 C 2 ion σ 2 , where Z' re This refers to the Warburg impedance (low-frequency impedance), R e R is the resistance of the electrolyte. ct For charge transfer resistance, σ w Here, ω is the Warburg coefficient, ω is the angular frequency, and R is the ideal gas constant (8.314 J / mol). -1 K -1 T is the temperature (K), n is the number of electrons transferred per mole, and F is the Faraday constant (96500°C mol). -1 A is the surface area of ​​the electrode (cm²) 2 ), and C ion For Li + molar concentration (mol m) -3 Warburg coefficient (σ) w ) can be derived from Z' re The slope is obtained. Briefly switch to Figures 6B to 6C By drawing from Figure 6B Z in the highlighted area re Values ​​of 1 / w 1 / 2 The curve of (angular frequency), σ w It can be obtained from the slope of the linear graph. Figure 6C ).

[0085] The cathode material of the present invention can have an improved σ-(Warberg coefficient) compared to cathode materials with the same active cathode material but formed by a method involving calcination. The coating formed by the calcination method can produce a thicker coating and therefore tends to have a larger σ-(Warberg coefficient) compared to the coating of the present invention.

[0086] In one embodiment, the cathode material may have a reversible discharge capacity under a voltage difference. In one aspect, the cathode material may be able to transition between a first crystal structure and a second crystal structure under a voltage difference, which can indicate the reversible discharge capacity of the cathode material. See also Figure 5B and Figure 5C Representative cathode materials can transition between a hexagonal crystal structure 500 and a monoclinic crystal structure 510, and can maintain the ability to transition between the two crystal structures 500 and 510 during the first charge-discharge cycle and one or more additional charge-discharge cycles. Both crystal structures include a TM layer 504 and a Li layer 502. In one specific aspect, the cathode material can be configured to maintain a similar ability to transition between crystal structures during the first charge-discharge cycle and one or more additional charge-discharge cycles. Figure 5C The figure includes a diagram of the differential capacity analysis of a representative cathode material S1. As shown, the cathode material S1 may be able to maintain its reversible discharge capacity for at least 1, 2, 3, 4, or 5 cycles.

[0087] In another embodiment, the cathode material may have a specific reversible discharge capacity under voltage difference, which may contribute to improved characteristics and / or performance of the cathode material. In another embodiment, the cathode material may have a specific coulombic efficiency that may contribute to improved characteristics and / or performance of the cathode material. Coulombic efficiency can represent the reversible discharge capacity of the cathode material. Coulombic efficiency can be defined as the measured discharge capacity C over cycle n. dis(n) Compared to the previously measured charging capacity C Ch(n) Technicians understand that for an ideal reversible discharge capacity, the coulombic efficiency should be approximately 100; and that the coulombic efficiency may decrease when some irreversible discharges occur.

[0088] In one embodiment, the cathode material has a coulombic efficiency of at least 70%, at least 75%, at least 78%, at least 80%, at least 85%, at least 88%, or at least 90% for at least one charge-recharge cycle. In a specific example, the coulombic efficiency may be close to 100% for at least one charge-recharge cycle, such as at least 93%, at least 95%, at least 97%, or at least 99%. In one particular aspect, the coulombic efficiency may be approximately 100% for at least one charge-recharge cycle. In another aspect, the cathode material may have a coulombic efficiency of at least 70% for at least two, three, four, or five charge-recharge cycles. In yet another aspect, the cathode material may have a coulombic efficiency of at least 80% for at least one, two, three, four, or five charge-recharge cycles. On the other hand, the cathode material may have a coulombic efficiency of at least 90% for at least 1 charge-discharge cycle, at least 2 charge-discharge cycles, at least 3 charge-discharge cycles, at least 4 charge-discharge cycles, or at least 5 charge-discharge cycles.

[0089] In another embodiment, the cathode material may contribute to improved electrolyte stability. See also Figure 5A In differential capacity analysis, cathode material CS2, which has the same active cathode material as S1 but without a coating, was tested. Small peaks were observed between 3.4V and 3.6V, which indicate the irreversible discharge capacity of the cathode material and the degradation of the electrolyte, regardless of the reversible discharge capacity indicated by the peaks between 3.5V and 3.9V.

[0090] Figure 4 The illustration includes a method 400 for forming a cathode material. Method 400 may include treating the active cathode material with a fluorinated material. In one embodiment, the fluorinated material may include organic materials, inorganic materials, or any combination thereof. In a specific embodiment, method 400 may include treating the active cathode material with an organic material containing the fluorinated material. Exemplary organic materials may include fluorocarbons. Examples of fluorocarbons may include hydrofluoroolefins, chlorofluorocarbons, hydrofluorocarbons, or fluorocarbons, or any combination thereof. Another fluorinated material may contain F2. In another example, a combination of two or more fluorinated materials may be used in method 400.

[0091] In one embodiment, the treatment of the active cathode material with a fluorine-containing material can be carried out at a relatively low temperature. For example, the temperature can be below 120°C, such as not exceeding 90°C, not exceeding 75°C, not exceeding 60°C, not exceeding 50°C, not exceeding 40°C, not exceeding 35°C, not exceeding 30°C, not exceeding 28°C, or not exceeding 25°C. In another example, the temperature can be at least 15°C, at least 18°C, at least 20°C, at least 22°C, or at least 25°C. Furthermore, the temperature can be within a range including any of the minimum and maximum values ​​described herein. In a specific embodiment, the treatment of the active cathode material with a fluorine-containing material can be carried out at a temperature ranging from at least 15°C to no more than 50°C or from at least 18°C ​​to no more than 35°C.

[0092] In one specific implementation, method 400 can be performed under dry conditions. In one aspect, the material that can contact the active cathode material can be a dry material. For example, the material can be a solid, a gas, or any combination thereof. In another example, method 400 may not involve a material comprising a liquid phase.

[0093] In one embodiment, the treatment of the active cathode material may be performed and last for at least 2 minutes and no more than 60 minutes, at least 5 minutes and no more than 40 minutes, at least 8 minutes and no more than 30 minutes, or at least 10 minutes and no more than 26 minutes.

[0094] The method may continue to block 404, thereby forming a coating covering at least a portion of the active cathode material. In one embodiment, forming the cathode material may include a chemical reaction between a fluorinated material and the active cathode material. In one specific aspect, the reaction may include fluorination of the active cathode material. In another aspect, the reaction may facilitate the deposition of a coating covering at least a portion of the active cathode material.

[0095] In one embodiment, method 400 may include a chemical vapor deposition method to form a coating covering the cathode active material. In another embodiment, method 400 may include using plasma to treat the active cathode material with a fluorine-containing material. In one specific example, radio frequency plasma may be used under a controlled gas pressure. For example, the gas pressure may be controlled in the range of 0.1 mbar to 1 mbar. In another specific example, the plasma may be a cryogenic plasma. In one example, the plasma may have a temperature not exceeding 100°C. In one specific example, the plasma may be less than 80°C, not exceeding 70°C, not exceeding 60°C, or not exceeding 50°C. In another example, the plasma may be excited by a frequency of 100 Hz to 1 GHz. In one specific embodiment, a plasma-enhanced chemical vapor deposition method may be used to form a cathode material comprising a coating covering the cathode active material. In another embodiment, method 400 may include utilizing gas treatment.

[0096] In one exemplary embodiment, the method for forming the cathode material can be carried out at room temperature (i.e., 22°C to 25°C). The active cathode material can be placed in a container and moved to a reaction chamber. Plasma can be used to treat the active cathode material with hydrofluoroolefins for 5 to 20 minutes to form a coated active cathode material. Specifically, the plasma can be cryogenic, such as below 80°C. In a more specific example, the plasma can contain electrons with higher energies (i.e., temperatures) than ions and neutral gaseous substances. The imbalance state of the plasma can favor the reaction used to form the coating. In another specific example, the plasma can be applied at low gas pressures (such as 0.1 mbar to 1 mbar) to favor the imbalance state of the plasma and the cryogenic temperature.

[0097] In another exemplary embodiment, a gaseous treatment using F2 can be performed. Specifically, the treatment can be carried out at room temperature up to 150°C. The active cathode material can be exposed to F2 gas between 0.03 bar and 3 bar for 10 minutes to 6 hours to form a coating.

[0098] Many different aspects and embodiments are possible. Some of those aspects and embodiments are described herein. After reading this specification, those skilled in the art will understand that those aspects and embodiments are merely exemplary and do not limit the scope of the invention. Embodiments may be made according to any one or more of the embodiments listed below.

[0099] Implementation Plan

[0100] Implementation Scheme 1. A cathode material comprising a substrate containing an active cathode material, wherein at least a portion of the substrate is covered with a CF-containing material. x Coating materials containing M2CO3, where M contains alkali metals.

[0101] Implementation Scheme 2. The cathode material according to Implementation Scheme 1, wherein M includes Li, Na, or combinations thereof.

[0102] Implementation Scheme 3. The cathode material according to Implementation Scheme 1 or 2, wherein the coating material further comprises MF.

[0103] Implementation Scheme 4. The cathode material according to any one of Implementation Schemes 1 to 3, wherein M comprises Li.

[0104] Implementation Scheme 5. The cathode material according to any one of Implementation Schemes 1 to 4, wherein the cathode active material comprises an oxide, the oxide comprising one or more metallic elements selected from alkali metals, 3d metals, 4d metals, 5d metals, rare earth metals and alkaline earth metals.

[0105] Implementation Scheme 6. The cathode material according to any one of Implementation Schemes 1 to 5, wherein the cathode active material comprises an alkali metal transition metal oxide.

[0106] Implementation Scheme 7. The cathode material according to Implementation Scheme 6, wherein the cathode active material comprises Li, Na, or a combination thereof.

[0107] Implementation Scheme 8. The cathode material according to Implementation Scheme 6 or 7, wherein the oxide comprises at least one 3d metal containing Ni.

[0108] Implementation Scheme 9. The cathode material according to Implementation Scheme 8, wherein the oxide comprises a Li-Ni-Mn oxide optionally doped with another 3d metal.

[0109] Implementation Scheme 10. The cathode material according to any one of Implementation Schemes 1 to 9, wherein the cathode active material comprises Li-Ni-Mn-Co oxide.

[0110] Implementation Scheme 11. The cathode material according to any one of Implementation Schemes 1 to 10, wherein the substrate comprises particles, the particles comprising the cathode active material.

[0111] Implementation Scheme 12. The cathode material according to any one of Implementation Schemes 1 to 11, wherein the coating material is in the form of a thin film that covers at least a majority of the substrate.

[0112] Implementation Scheme 13. The cathode material according to any one of Implementation Schemes 1 to 12, wherein the substrate is in the form of a strip, sheet, film, block, or any combination thereof.

[0113] Implementation Scheme 14. The cathode material according to any one of Implementation Schemes 1 to 13, wherein the cathode material comprises not more than 2940 Ωs -1 Not greater than 2800Ωs -1 Not greater than 2500Ωs -1 Not greater than 2200Ωs -1 Not greater than 2000Ωs -1 1800Ωs -1 1600Ωs -1 1490Ωs -1 or not greater than 1350Ωs -1 σ-(Warberg coefficient).

[0114] Implementation Scheme 15. The cathode material according to any one of Implementation Schemes 1 to 14, wherein the cathode material comprises at least 500 Ωs -1 At least 700Ωs -1 At least 850Ωs-1 At least 1000Ωs -1 At least 1150Ωs -1 At least 1300Ωs -1 or at least 1400Ωs -1 σ-(Warberg coefficient).

[0115] Implementation Scheme 16. A cathode material according to any one of Implementation Schemes 1 to 15, wherein the cathode material has an M2CO3 to CF ratio of at least 3.6, at least 3.8, at least 4.1, at least 4.5, at least 4.8, at least 5.1, at least 5.3, at least 5.7, at least 5.9, at least 6.3, at least 6.7, at least 6.9, at least 7.2, at least 7.5, at least 7.8, at least 8.1, at least 8.3, at least 8.5, or at least 8.7. x The content ratio of C1.

[0116] Implementation Scheme 17. The cathode material according to any one of Implementation Schemes 1 to 16, wherein the cathode material has an M2CO3 to CF ratio of not greater than 11.5, not greater than 11.2, not greater than 10.8, not greater than 10.5, not greater than 10.1, not greater than 9.7, not greater than 9.4, not greater than 9.1, not greater than 8.8, not greater than 8.6, or not greater than 8.3. x The content ratio of C1.

[0117] Implementation Scheme 18. The cathode material according to any one of Implementation Schemes 1 to 17, wherein the cathode material comprises a relative content of at least 0.4, at least 0.6, at least 0.7, at least 0.8, at least 0.9, or at least 1.0 of M2CO3.

[0118] Implementation Scheme 19. The cathode material according to any one of Implementation Schemes 1 to 18, wherein the cathode material contains a relative content of M2CO3 of not more than 1.5, not more than 1.3, not more than 1.1, not more than 0.9, or not more than 0.8.

[0119] Implementation Scheme 20. The cathode material according to any one of Implementation Schemes 1 to 19, wherein the cathode material comprises at least 0.05, at least 0.07, at least 0.09, at least 0.11, or at least 0.13% CF x The relative content of.

[0120] Implementation Scheme 21. The cathode material according to any one of Implementation Schemes 1 to 20, wherein the cathode material comprises CF at a concentration not greater than 0.42, 0.40, 0.38, 0.35, 0.32, 0.30, 0.28, 0.27, 0.25, 0.23, 0.21, 0.18, 0.15, or 0.13. x The relative content of.

[0121] Implementation Scheme 22. The cathode material according to any one of Implementation Schemes 1 to 21, wherein the cathode material has an MF to M2CO3 content ratio C2 of at least 1.2, at least 1.4, at least 1.6, at least 1.8, at least 2.1, at least 2.3, at least 2.5, at least 2.7, at least 2.9, at least 3.0, or at least 3.2.

[0122] Implementation Scheme 23. The cathode material according to any one of Implementation Schemes 1 to 22, wherein the cathode material has an MF to M2CO3 content ratio C2 of not more than 6.4, not more than 6.1, not more than 5.8, not more than 5.5, not more than 5.2, not more than 4.9, not more than 4.6, not more than 4.3, not more than 4.1, not more than 3.8, not more than 3.5, not more than 3.2, not more than 3.1, or not more than 2.9.

[0123] Implementation Scheme 24. A cathode material according to any one of Implementation Schemes 1 to 23, the cathode material having an MF and CF of at least 6.3, at least 7.8, at least 9.2, at least 10.5, at least 11.1, at least 12.3, at least 14.5, at least 15.2, at least 16.9, at least 18.0, at least 19.5, at least 21.5, at least 23.8, at least 24.5, at least 25.8, or at least 26.2. x The content ratio of C3.

[0124] Implementation Scheme 25. The cathode material according to any one of Implementation Schemes 1 to 24, wherein the cathode material has an MF and CF of not greater than 35.4, not greater than 34.1, not greater than 32.8, not greater than 31.5, not greater than 30.2, not greater than 28.9, not greater than 28.6, not greater than 27.3, not greater than 26.1, not greater than 25.8, or not greater than 24.5. x The content ratio of C3.

[0125] Implementation Scheme 26. A cathode material according to any one of Implementation Schemes 1 to 25, wherein the cathode material comprises a relative content of at least 1.2, at least 1.4, at least 1.7, at least 1.9, at least 2.1, at least 2.3, at least 2.5, at least 2.7, at least 2.9, at least 3.0, or at least 3.2 of MF.

[0126] Implementation Scheme 27. The cathode material according to any one of Implementation Schemes 1 to 26, wherein the cathode material comprises a relative content of MF not greater than 6.4, not greater than 6.1, not greater than 5.8, not greater than 5.5, not greater than 5.2, not greater than 4.9, not greater than 4.6, not greater than 4.2, not greater than 3.9, not greater than 3.7, not greater than 3.5, not greater than 3.1, or not greater than 3.0.

[0127] Implementation Scheme 28. A multilayer structure comprising a cathode layer covering an electrolyte layer, wherein the cathode layer comprises a cathode material according to any one of claims 1 to 27.

[0128] Implementation Scheme 29. The multilayer structure according to Implementation Scheme 28, wherein the cathode layer is adjacent to the electrolyte layer, and wherein the coating material is in direct contact with the electrolyte layer.

[0129] Implementation Scheme 30. The multilayer structure according to Implementation Scheme 28 or 29, wherein the electrolyte layer comprises a solid electrolyte material, wherein the solid electrolyte material comprises a halide material.

[0130] Implementation Scheme 31. A material comprising a solid electrolyte material and a cathode material according to any one of Implementation Schemes 1 to 27, wherein the solid electrolyte material comprises a halide material.

[0131] Implementation Scheme 32. A multilayer structure or material according to any one of Implementation Schemes 30 to 31, wherein the halide material comprises a material selected from the group consisting of F, Cl, Br and I and is composed of Li 3-x-f M f RE 1-y Me k y (Cl 1-u-p- q Br u F p I q ) 6-x+y*(k-3) The halide anion is represented.

[0132] in:

[0133] -1 <= x <= 1;

[0134] 0 <= y <= 1;

[0135] 0 <= u < 1;

[0136] 0 <= p <= 1 / 3;

[0137] 0 <= q <= 1 / 6;

[0138] 0 < (u + p + q) < 1;

[0139] 0 <= f <= 0.3;

[0140] M is at least one alkali metal element other than Li;

[0141] RE is a rare earth element;

[0142] k is the valence of Me; and

[0143] Me is at least one element selected from the group consisting of elements of group IIIB, group IVB, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Al, Sn, Pb, Bi, Sb, Mg, Ca, Ga, and Ge, wherein Me is different from RE.

[0144] Implementation Scheme 33. A multilayer structure or material according to any one of Implementation Schemes 28 to 32, wherein the electrolyte material comprises a halide material comprising at least two halide anions selected from the group consisting of F, Cl, Br and I.

[0145] Implementation Scheme 34. A multilayer structure or material according to any one of Implementation Schemes 30 to 33, wherein the halide material comprises, by weight of the total halide material:

[0146] One or more water-insoluble impurity phases in a total content of less than 0.11% by weight;

[0147] A total content of no more than 10% by weight of a binary halide phase;

[0148] Not more than 6% by weight of ternary halide phase; or

[0149] Any combination of them.

[0150] Implementation Scheme 35. A multilayer structure according to any one of Implementation Schemes 30 to 34, wherein the halide material is made of Li 3-x RE 1-y Me k y (Cl 1-u Br u ) 6-x+y*(k-3) This indicates that 0.08 <= u <= 0.67.

[0151] Implementation Scheme 36. A multilayer structure or material according to any one of Implementation Schemes 30 to 35, wherein the halide material is made of Li a M a Me b Me' b’ X c X' c’This indicates that the halide material exhibits a crystallographic phase transition within the following stoichiometric range:

[0152] (b / (b+b')) t *0.84 t *1.16, where (b / (b+b')) t This corresponds to the crystallographic phase transition on the crystallographic phase diagram at temperatures between 20°C and 25°C.

[0153] (c / (c+c')) t *0.84 <c / (c+c')<(c / (c+c')) t *1.16, where (c / (c+c')) t This corresponds to the crystallographic phase transition on the crystallographic phase diagram at temperatures between 20°C and 25°C; or

[0154] (a / (a+a')) t *0.84 t *1.16, among which (a / (a+a')) t This corresponds to the crystallographic phase transition on the crystallographic phase diagram at temperatures between 20°C and 25°C.

[0155] Implementation Scheme 37. A multilayer structure or material according to any one of Implementation Schemes 1 to 36, wherein the cathode material is capable of transitioning between a hexagonal crystal structure and a monoclinic crystal structure under a voltage difference.

[0156] Implementation Scheme 38. A multilayer structure or material according to any one of Implementation Schemes 1 to 37, wherein the cathode material has a reversible discharge capacity under voltage difference, wherein the cathode material has a coulombic efficiency of at least 70%, at least 75%, at least 78%, at least 80%, at least 85%, at least 88%, at least 90%, close to 100%, or 100%.

[0157] Implementation Scheme 39. A method comprising treating a cathode active material with an organic material comprising a fluorine-containing material at a temperature below 120°C.

[0158] Implementation Scheme 40. The method according to Implementation Scheme 39, wherein the treatment of the cathode active material is carried out under dry conditions.

[0159] Implementation Scheme 41. The method according to Implementation Scheme 39 or 40, wherein the fluorinated material includes organic materials, inorganic materials, or any combination thereof.

[0160] Implementation Scheme 42. The method according to any one of Implementation Schemes 39 to 41, wherein the fluorinated material comprises a fluorocarbon compound.​​

[0161] Implementation Scheme 43. The method according to any one of Implementation Schemes 39 to 42, wherein the fluorinated material comprises hydrofluoroolefins, chlorofluorocarbons, hydrofluorocarbons or fluorocarbons, or any combination thereof.

[0162] Implementation Scheme 44. The method according to any one of Implementation Schemes 39 to 41, wherein the fluorinated material contains F2.

[0163] Implementation Scheme 45. The method according to any one of Implementation Schemes 39 to 44, the method comprising treating the cathode active material with plasma.

[0164] Implementation Scheme 46. The method according to Implementation Scheme 45, wherein the plasma is excited by a frequency of 100 Hz to 1 GHz.

[0165] Implementation Scheme 47. The method according to Implementation Scheme 45 or 46, wherein the plasma is applied at a gas pressure of at least 0.1 mbar and at most 1 mbar.

[0166] Implementation Scheme 48. The method according to any one of Implementation Schemes 39 to 47, wherein the treatment of the cathode active material is performed and sustained for at least 2 minutes to no more than 60 minutes, at least 5 minutes to no more than 40 minutes, at least 8 minutes to no more than 30 minutes, or at least 10 minutes to no more than 26 minutes.

[0167] Implementation Scheme 49. The method according to any one of Implementation Schemes 39 to 48, wherein the treatment of the cathode active material is carried out at a temperature not exceeding 90°C, not exceeding 75°C, not exceeding 60°C, not exceeding 50°C, not exceeding 40°C, not exceeding 30°C, or not exceeding 28°C.

[0168] Implementation Scheme 50. The method according to any one of Implementation Schemes 39 to 49, wherein the treatment of the cathode active material is carried out at a temperature of at least 15°C, at least 20°C, or at least 22°C.

[0169] Implementation Scheme 51. The method according to any one of Implementation Schemes 39 to 50, wherein processing the cathode active material comprises a chemical vapor deposition method.

[0170] Implementation Scheme 52. The method according to any one of Implementation Schemes 39 to 51, wherein processing the cathode active material comprises a plasma-enhanced chemical vapor deposition method.

[0171] Example

[0172] Example 1

[0173] According to the embodiments described herein, the active cathode material NMC622 is fluorinated using hydrofluoroolefins and plasma-enhanced chemical vapor deposition (PE-CVD) to form coated NMC622. Uncoated NMC622 and coated NMC622 are then reacted with Li3Y(Cl... 0.65 Br 0.35 6 and conductive carbon are pressed together into granules and used as cathodes in a unit cell, which includes a lithium foil anode and Li3Y(Cl) 0.65 Br 0.35 6. Electrolyte composed of pressed granules. Battery 1 contains uncoated NMC622. Battery 2 contains coated NMC622. XPS confirmed that the coated NMC622 includes a coating containing CF x LiF and Li2CO3; and the uncoated NMC622 does not contain fluorine-containing substances. The cathode comprises the cathode material and Li3Y(Cl... 0.65 Br 0.35 )60% by weight of the corresponding cathode material and 40% by weight of Li3Y(Cl) 0.65 Br 0.35 6% and 0.5% by weight of conductive carbon.

[0174] The specific capacity (relative to Li / Li) of battery pack cell 1 and battery pack cell 2 was tested at voltages ranging from 3V to 4.2V. + The summarized data for battery pack unit 1 and battery pack unit 2 are included in Table 1 and Table 2, respectively.

[0175] Table 1 (Battery pack cell 1 including uncoated NMC622)

[0176] 1 166.66 114.48 68.89％ 2 109.28 107.24 98.14％ 3 104.05 102.87 98.86％

[0177] Table 2 (including battery pack cell 2 with coated NMC622)

[0178] 1 174.96 150.05 86％ 2 152.41 148.41 97％ 3 150.47 147.60 98％

[0179] Under cycle 1, compared to cell 1, cell 2 exhibits improved maximum charge and maximum discharge capacity and improved coulombic efficiency (CE%) across all charge-discharge cycles. The low coulombic efficiency of the cathode material in cell 1 indicates electrolyte degradation and irreversible discharge during lithiation and delithiation. The higher coulombic efficiency of the coated cathode material in cell 2 indicates improved reversible discharge capacity and significantly reduced electrolyte degradation.

[0180] Example 2

[0181] According to the embodiments described herein, an active cathode material NMC622 is treated with hydrofluoroolefin (HFO) using plasma-enhanced chemical vapor deposition (PE-CVD) to form a coated NMC622. The plasma treatment time is varied to form different coated NMC622 samples. Coated NMC622 sample S3 is formed by plasma treatment for 5 minutes. Coated NMC622 sample S4 is formed by plasma treatment for 10 minutes. Coated NMC622 sample S5 is formed by plasma treatment for 20 minutes. Similar to Example 1, XPS is used to confirm the coated NMC622 samples including the coating, which comprises CF1, LiF, and Li2CO3.

[0182] Uncoated NMC622 and all coated NMC622 samples were used to form cathodes in a manner similar to Example 1, and were used as cathodes in a battery comprising a lithium foil anode and Li3Y(Cl) 0.65 Br 0.35 The electrolyte is composed of pressed granules of NMC622. Battery 3 contains coated NMC622 S3. Battery 4 contains coated NMC622 S4. Battery 5 contains coated NMC622 S5. Battery 6 is formed using uncoated NMC622. The cathode contains a cathode material and Li3Y(Cl) 0.65 Br 0.35 )60% by weight of the corresponding cathode material and 40% by weight of Li3Y(Cl) 0.65 Br 0.35 6% and 0.5% by weight of conductive carbon.

[0183] The specific capacity of the battery pack cells was tested, and in Figure 5A (Battery pack unit 6) and Figure 5C (Example in battery pack cell 4). It can be observed that... Figure 5A The irreversible discharge capacity illustrated in the figure indicates that electrolyte degradation was inhibited by the coated sample 6, because... Figure 5C There are no small peaks in the 3.4V to 3.6V range. For example... Figure 5A As shown, the smaller peaks at 3.4V to 3.6V indicate irreversible discharge capacity and electrolyte degradation.

[0184] Differential capacity analysis was performed on the battery pack cells for up to 5 charge-discharge cycles, and the results were summarized in... Figure 5D In the middle. For example Figure 5DAs illustrated, compared to battery cell 6, battery cell 4 exhibits improved initial capacity (cycle 1) and improved specific capacity, with an increased number of cycles. The data further demonstrates that, with increased cycle count, the capacity degradation of battery cell 6 and the capacity retention of cell 4 are improved.

[0185] Figure 6A The graph shows the specific capacity versus cycle life for battery cells 3 to 5. It can be observed that all battery cells 3 to 5 exhibit improved specific capacity and capacity retention during the test cycles. Compared to cells 3 and 5, cell 4 may have a further improved specific capacity; and cell 3 may have an improved specific capacity than cell 5. Compared to cell 6, cell 5 does not show an improvement in specific capacity, but it has an improved capacity retention (not shown) during the test cycles.

[0186] Figure 6B Including battery pack cells 3 to 5 using linear frequency -Z lmag For Z re The graph shows that cathode material S4 has a higher ion diffusion Warburg impedance than cathode material S3. Figure 6B The Zre value in the highlighted area is relative to ω. -1 / 2 The curves extracted from the plot ( Figure 6C Z shown re Relative to ω -1 / 2 (The curve is shown). The data indicates that, compared to cathode materials S3 and S4, cathode material S5 can have the lowest Li. + The ion diffusion rate, and cathode material S4 can have a higher Li content than cathode material S3. + Ion diffusion rate.

[0187] The σ-(Warberg coefficient) of cathode materials S3 to S5 are calculated according to the implementation scheme described herein and are included in Table 3 below.

[0188] Table 3

[0189] S3 1493 S4 1313 S5 2943

[0190] CF of cathode materials S3 to S5 x The relative contents of LiF and Li2CO3 were determined by running XPS on samples with sample sizes statistically representative of samples S3 to S5 as described in the embodiments herein. The relative contents (relative to Ni content) are included in Table 4 below. No fluorides (fluorinated carbon and LiF) were detected in the uncoated NMC622 samples using high-resolution XPS spectroscopy with F1s.

[0191] The concentrations of organic and inorganic fluorides in samples S3 to S5 were assessed and determined based on the corresponding ratio of organic fluorides (fluorinated carbon) to inorganic fluorides (LiF) obtained by high-resolution XPS spectroscopy using F1s, and the total concentrations of organic and inorganic fluorides obtained by ion chromatography. Organic fluorides have a binding energy peak at 689 eV, and inorganic fluorides have binding energy peaks between 681 eV and 682 eV. Concentrations are included in Table 5. The total concentration is the weight of all fluorides relative to the sample weight; and the concentrations of organic and inorganic fluorides are the respective weights relative to the sample weight.

[0192] Table 4

[0193] S3 0.264 1.637 1.470 5.57 S4 0.111 2.866 0.944 8.504 S5 0.105 2.358 0.367 3.495

[0194] Table 5

[0195]

[0196] Example 3

[0197] A set of cathode materials from sample S4 of Example 2 was heated at 500°C to remove carbonaceous material and form sample S9. Sample S9 was analyzed using high-resolution XPS spectroscopy with F1s, and it was confirmed that no fluorinated carbon was detected. Except for using sample S9 to form the cathode, battery cell 9 was formed in a manner similar to that described in Example 2.

[0198] Figure 7 The graph shows the specific capacity versus cycle number for battery cells 4 and 9. It can be observed that battery cell 9 has a lower specific capacity compared to battery cell 4, suggesting that carbon fluoride can improve battery performance.

[0199] Example 4

[0200] According to the embodiments described herein, the active cathode material NMC811 (LiNi) is fluorinated using hydrofluoroolefins and plasma-enhanced chemical vapor deposition (PE-CVD). 0.8 Mn 0.1 Co 0.1 O2) to form coated NMC811. Uncoated NMC811 and coated NMC811 are then reacted with Li3Y(Cl) 0.65 Br 0.35 Lithium oxide (Li₂) and conductive carbon are pressed together into granules and used as cathodes in a single-cell battery, which includes a lithium foil anode and Li₃Y(Cl₂)₆. 0.65 Br0.35 6. Electrolyte composed of pressed granules. Cell sample S10 contains uncoated NMC811. Cell sample S11 contains coated NMC811. The cathode comprises the cathode material and Li3Y(Cl...) 0.65 Br 0.35 )60% by weight of the corresponding cathode material and 40% by weight of Li3Y(Cl) 0.65 Br 0.35 6% and 0.5% by weight of conductive carbon.

[0201] Figure 8 The graphs show the specific capacity versus voltage for battery cell samples S10 and S11. Sample S11 exhibits superior specific capacity stability over the test voltage range compared to sample S10.

[0202] The benefits, other advantages, and solutions to problems have been described above with respect to specific embodiments. However, the benefits, advantages, solutions to problems, and any features that may cause any benefit, advantage, or solution to appear or become more significant should not be construed as key, essential, or necessary features of any or all claims. The term "material comprising one or more components" as mentioned herein can be interpreted as including at least one embodiment in which the material is substantially composed of the identified one or more components. The term "substantially composed of" will be interpreted as including a composition comprising the identified materials and excluding all other materials except for a few contents (e.g., impurity contents) that do not significantly alter the properties of the material. Furthermore, references to values ​​stated in the range include each value within that range. Additionally, or in alternative embodiments, in some non-limiting embodiments, any of the compositions identified herein may be substantially free of materials not explicitly disclosed. The embodiments herein include ranges of the content of certain components within the material, and it should be understood that the total content of the components within a given material is 100%.

[0203] The description and illustrations of the embodiments described herein are intended to provide a general understanding of the structure of various embodiments. The description and illustrations are not intended to be an exhaustive and comprehensive description of all elements and features of devices and systems using the structures or methods described herein. Individual embodiments may also be provided in combination in a single embodiment, and conversely, various features described in the context of a single embodiment for brevity may also be provided individually or in any sub-combination. Furthermore, references to values ​​stated in the scope include every value within that scope. Many other embodiments may be apparent to a person skilled in the art only after reading this specification. Other embodiments may be used and derived from this disclosure, such that structural substitutions, logical substitutions, or other changes may be made without departing from the scope of this disclosure. Therefore, this disclosure should be considered illustrative rather than restrictive.

Claims

1. A cathode material comprising a substrate containing an active cathode material, wherein at least a portion of the substrate is coated with a material containing fluorinated carbon (CF4). x A coating material containing M2CO3 and M2CO3, wherein M comprises an alkali metal, said alkali metal comprising Li, Na, or a combination thereof, wherein the relative content of M2CO3 is related to that of fluorinated carbon (CF2CO3). x The ratio of the relative contents of M2CO3 and CF is at least 3.6 and not more than 11.5, wherein the relative contents of M2CO3 and CF are... x The relative contents are compared with the Ni content determined by XPS.

2. The cathode material according to claim 1, wherein the active cathode material comprises an alkali metal transition metal oxide.

3. The cathode material according to claim 1, wherein the coating material further comprises MF.

4. The cathode material according to any one of claims 1 to 3, wherein M comprises Li.

5. The cathode material according to any one of claims 1 to 3, wherein the active cathode material comprises a Li-Ni-Mn oxide optionally doped with another 3d metal.

6. The cathode material according to any one of claims 1 to 3, wherein the substrate comprises particles, and the particles comprise the active cathode material.

7. The cathode material according to any one of claims 1 to 3, wherein the coating material is in the form of a thin film covering at least a majority of the substrate, wherein the substrate is in the form of a strip, sheet, film, block, or any combination thereof.

8. The cathode material according to any one of claims 1 to 3, wherein the fluorinated carbon comprises CF1.

9. The cathode material according to claim 3, wherein the concentration ratio of inorganic fluoride to organic fluoride in the cathode material is greater than 22.

5.

10. The cathode material according to claim 3, wherein the cathode material has a total fluoride concentration of less than 805 µg / g relative to the weight of the active cathode material, an inorganic fluoride concentration of greater than 202.3 µg / g, or a combination thereof.

11. A multilayer structure comprising a cathode layer covering an electrolyte layer, wherein the cathode layer comprises the cathode material according to claim 1.

12. The multilayer structure of claim 11, wherein at least a portion of the coating material is in direct contact with the electrolyte layer, wherein the electrolyte layer comprises a solid electrolyte material, the solid electrolyte material comprising Li 3-x- f M f RE 1-y Me k y (Cl 1-u-p-q Br u F p I q ) 6-x+y*(k-3) The material represented is based on halides. in: -1≤x≤1； 0≤y≤1； 0≤u<1； 0≤p≤1 / 3； 0≤q≤1 / 6； 0 < (u + p + q) < 1; 0≤f≤0.3； 2≤k≤6； M is at least one alkali metal element other than Li; RE is a rare earth element; k is the valence of Me; and Me is at least one element selected from the group consisting of elements of group IIIB, group IVB, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Al, Sn, Pb, Bi, Sb, Mg, Ca, Ga, and Ge, wherein Me is different from RE.

13. The multilayer structure according to claim 12, wherein the halide material comprises at least two halogens.

14. A material comprising a solid electrolyte material and a cathode material according to claim 1, wherein the solid electrolyte material comprises Li 3-x-f M f RE 1-y Me k y (Cl 1-u-p-q Br u F p I q ) 6-x+y*(k-3) The material represented is based on halides. in: -1≤x≤1； 0≤y≤1； 0≤u<1； 0≤p≤1 / 3； 0≤q≤1 / 6； 0 < (u + p + q) < 1; 0≤f≤0.3； 2≤k≤6； M is at least one alkali metal element other than Li; RE is a rare earth element; k is the valence of Me; and Me is at least one element selected from the group consisting of elements of group IIIB, group IVB, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Al, Sn, Pb, Bi, Sb, Mg, Ca, Ga, and Ge, wherein Me is different from RE.

15. A method for forming a cathode material according to any one of claims 1-10, the method comprising treating the active cathode material with an organic material containing a fluorine-containing material at a temperature below 120°C, wherein the fluorine-containing material comprises hydrofluoroolefins, chlorofluorocarbons, hydrofluorocarbons or fluorocarbons, or any combination thereof.

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