Ytterbium-containing solid lithium ion conductive material and method for preparing same

Abstract

The present invention describes a solid-state material having ionic conductivity for lithium ions, a composite comprising said solid-state material and a positive electrode active material, a method for preparing said solid-state material, the use of said solid-state material as a solid electrolyte in an electrochemical cell, a solid structure selected from the group consisting of a positive electrode (cathode), a negative electrode (anode) and a separator of an electrochemical cell comprising said solid-state material, and an electrochemical cell comprising such a solid-state structure.

Description

Technical Field

[0001] A solid material having ionic conductivity with respect to lithium ions, a composite including the solid material and a cathode active material, a method for preparing the solid material, use of the solid material as a solid electrolyte of an electrochemical cell, a cathode (positive electrode), an anode (negative electrode) of an electrochemical cell including the solid material, and a solid structure selected from the group consisting of a separator, and an electrochemical cell including such a solid structure will be described.

Background Art

[0002] With the spread of all-solid-state lithium batteries, the demand for solid electrolytes having high conductivity with respect to lithium ions has been increasing. An important one among such solid electrolytes is lithium transition metal halides.

[0003] US2019 / 0088995A1 discloses a solid electrolyte material represented by the composition formula: Li 6-3z Y z X6 (satisfying 0 < z < 2; X represents Cl or Br). According to US2019 / 0088995A1, these materials exhibit ionic conductivity in the range of 0.2 * 10 -4 S / cm to 7.1 * 10 -4 S / cm at around room temperature.

[0004] Further prior art is US2020 / 328463A1, by Andreas Bohnsack et al., Zeitschrift fuer anorganische und allgemeine Chemie (Journal of Inorganic and General Chemistry) Vol. 623, September 1, 1997, pages 1067 - 1073 and 1352 - 1356.

Prior Art Documents

Patent Documents

[0005] [Patent Document 1] US2019 / 0088995A1 [Patent Document 2] US2020 / 328463A1 [Non-patent literature]

[0006] [Non-Patent Document 1] Andreas Bohnsack et al., Zeitschrift fuer anorganische und allgemeine Chemie (Journal of Inorganic and General Chemistry), Volume 623, September 1, 1997, pages 1067-1073 and 1352-1356 [Brief explanation of the drawings]

[0007] [Figure 1] Figure 1 shows the X-ray diffraction (XRD) patterns of Li3-xYb1-xZrxCl6 materials ranging from x=0 to x=0.5 (see Table 1 below) obtained by heat treatment at 350°C. [Figure 2] FIG. 2 shows the cyclic voltammogram of the all-solid-state battery with the configuration defined above. [Figure 3] FIG. 3 shows the first (solid line) and second (dashed line) charge-discharge profiles (0.1 C) of the above-defined all-solid-state battery with the following composition: (mixture of LiCoO and LiYbZrCl)|LiPS|Li-In alloy. [Figure 4] Figure 4 shows the charge / discharge capacity as a function of cycle number at different C rates. The battery exhibits high coulombic efficiency and good capacity retention. Summary of the Invention [Problem to be solved by the invention]

[0008] It exhibits ionic conductivity suitable for use as a solid electrolyte in all-solid-state lithium batteries, and V vs. Li / Li of 4 or more can be obtained to obtain a high battery voltage. + To enable the application of cathode active materials with redox potentials of 4V class (cathode active materials), + , preferably 4.5V vs. Li / Li + There is a continuing need for solid lithium ion conductors that exhibit the above electrochemical oxidative stability.

[0009] It is an object of the present disclosure to provide a solid-state material that can be used as a solid electrolyte in an electrochemical cell. More specifically, it is an object of the present disclosure to provide a solid-state material that can be used as a solid electrolyte in an electrochemical cell, the positive electrode of which is 4 V vs. Li / Li. + The positive electrode active material has an oxidation-reduction potential of at least 1000 ppm.

[0010] Further provided are composites comprising the solid material and a positive electrode active material, methods for preparing the solid material, uses of the solid material as a solid electrolyte in electrochemical cells, solid structures selected from the group consisting of positive electrodes, negative electrodes and separators of electrochemical cells comprising the solid material, and electrochemical cells having such solid structures, wherein the solid structure comprises the solid material. [Means for solving the problem]

[0011] According to a first aspect, the general formula (I) Li 3-n*x Yb 1-x M x X y (I) (In the formula, 0.05 ≤ x ≤ 0.95; 5.8 ≤ y ≤ 6.2; n is the difference in valence between M and Yb; M is one or more selected from the group consisting of Ti, Zr, Hf, V, Nb, and Ta; X is one or more selected from the group consisting of halides and pseudohalides. A solid material is provided having a composition given by:

[0012] Since ytterbium is trivalent, n is 1 when M is tetravalent (Ti, Zr, Hf), and n is 2 when M is pentavalent (Ta, Nb, V).

[0013] The compositions according to general formula (I) can be considered as lithium transition metal halides or as lithium transition metal pseudohalides.

[0014] As used herein, the term "pseudohalides" (also called "pseudohalogenides") refers to monovalent anions that are similar in chemistry to halide anions and thus can replace halide anions in chemical compounds without substantially changing the properties of such compounds. The term "pseudohalide ion" is known in the art; see the IUPAC Goldbook. Examples of pseudohalide anions include N3 - , SCN - , C.N. - , OCN - , BF4 - , BH4 - In the case of the pseudohalide-containing solid material of general formula (I), the pseudohalide anion is preferably BF4 - and BH4 - is selected from the group consisting of:

[0015] In the case of halide-containing solid materials of general formula (I), the halide is preferably selected from the group consisting of Cl, Br and I.

[0016] Surprisingly, the solid material having a composition according to the general formula (I) defined above has a V vs. Li / Li ratio of 4 or more. + We have found that these electrolytes can exhibit good lithium ion conductivity along with electrochemical oxidation stability in contact with cathode active materials having redox potentials of 0.1 to 1.0 V, and also in contact with electronically conducting materials containing or consisting of elemental carbon (e.g., carbon black, graphite), a typical electrode additive in electrochemical cells, which is a significant advantage over current state-of-the-art sulfur-containing solid electrolytes.

[0017] The solid material according to the first aspect defined herein may have a composition according to formula (I), wherein X is one or more halides selected from the group consisting of Cl, Br and I, preferably Cl.

[0018] The solid material according to the first aspect defined herein may have a composition according to formula (I), wherein 0.08≦x≦0.85, preferably 0.1≦x≦0.8, more preferably 0.12≦x≦0.65, and most preferably 0.15≦x≦0.6.

[0019] The solid material according to the first aspect defined herein may have a composition according to formula (I), wherein 5.85≦y≦6.15, more preferably 5.9≦y≦6.1, most preferably 5.95≦y≦6.05.

[0020] More specifically, the solid material according to the first aspect defined herein may have a composition according to formula (I), wherein 0.08≦x≦0.85, preferably 0.1≦x≦0.8, more preferably 0.12≦x≦0.65, and most preferably 0.15≦x≦0.6, and 5.85≦y≦6.15, preferably 5.9≦y≦6.1, and most preferably 5.95≦y≦6.05.

[0021] More particularly, the solid material according to the first aspect defined herein may have a composition according to formula (I), wherein: - X is one or more halides selected from the group consisting of Cl, Br and I, preferably Cl; and 0.05≦x≦0.95, more particularly 0.08≦x≦0.85, preferably 0.1≦x≦0.8, more preferably 0.12≦x≦0.65, most preferably 0.15≦x≦0.6; and 5.8≦y≦6.2, more particularly 5.85≦y≦6.15, preferably 5.9≦y≦6.1, most preferably 5.95≦y≦6.05.

[0022] In some cases, a solid material according to the first aspect defined herein may be crystalline, detectable by X-ray diffraction techniques. A solid material is said to be crystalline if it exhibits the long-range order characteristic of crystals, as indicated by the presence of well-defined reflections in its X-ray diffraction pattern. In this case, a reflection is considered well-defined if its intensity is more than 10% higher than background.

[0023] The solid material according to the first aspect defined above can consist of a single phase or two or more phases, such as a major phase (primary phase) and trace amounts of impurities and secondary phases. It is understood that formula (I) is an empirical formula (total formula) determinable by means of elemental analysis. Thus, formula (I) defines the average composition for all phases present in the solid material. However, the solid material according to the first aspect defined above contains at least one phase having a composition according to formula (I). When the crystalline solid material according to the first aspect defined above contains more than one phase, the mass fraction of such phases not having a composition according to formula (I) (e.g., impurity phase, secondary phase) is so small that the composition averaged over all phases conforms to formula (I). The total mass fraction of the secondary and impurity phases may be 20% or less, preferably 10% or less, more preferably 5% or less, and most preferably 3% or less, based on the total mass of the solid material.

[0024] If present, the secondary and impurity phases consist mainly of the precursors used to prepare the solid material, e.g., LiX and MX3 (where X and M are as defined above), and sometimes impurity phases that may originate from precursor impurities. For details of the preparation of the solid material according to the first aspect defined above, please refer to the information provided below in the context of the second aspect of the present disclosure.

[0025] In certain cases, the solid material according to the first aspect defined above is in the form of a polycrystalline powder or in the form of a single crystal.

[0026] The crystalline solid state material according to the first aspect as defined herein may comprise or consist of one or more crystalline phases having a structure selected from an orthorhombic structure of space group Pnma, and a trigonal structure of space group P-3m1.

[0027] In certain cases, the solid material according to the first aspect defined herein is glassy, ​​i.e., amorphous. A solid material is said to be amorphous if it lacks the long-range order characteristic of a crystal, as indicated by the absence of clearly defined reflections in an X-ray diffraction pattern. In this context, a reflection is considered well-defined if its intensity is more than 10% higher than the background.

[0028] In certain cases, the solid material according to the first aspect as defined herein is a glass-ceramic, i.e. a polycrystalline solid having at least 30% by volume of a glassy phase.

[0029] A first group of solid state materials according to a first aspect defined herein has a composition according to formula (I), where X is as defined above; and M is one or more of Ti, Zr, and Hf. In said first group of solid state materials, M is a tetravalent metal and n is 1. Thus, said first group of solid state materials has a composition according to formula (Ia): Li 3-x Yb 1-x M x X y (Ia) (In the formula, M is one or more selected from the group consisting of Ti, Zr, and Hf; X is one or more selected from the group consisting of halides and pseudohalides; 0.05 ≤ x ≤ 0.95; 5.8≦y≦6.2) The composition is as follows:

[0030] The first group of solid materials defined above may have a composition according to formula (Ia), where X is one or more halides selected from the group consisting of Cl, Br, and I. More specifically, the first group of solid materials defined above may have a composition according to formula (Ia), where X is Cl.

[0031] The first group of solid materials defined above may have a composition according to formula (Ia), where M is Zr. More specifically, the first group of solid materials defined above may have a composition according to formula (Ia), where M is Zr and X is one or more halides selected from the group consisting of Cl, Br and I, preferably Cl.

[0032] The first group of solid materials defined above may have a composition according to formula (Ia), wherein 0.08≦x≦0.85, preferably 0.1≦x≦0.8, more preferably 0.12≦x≦0.65, and most preferably 0.15≦x≦0.6.

[0033] The first group of solid materials defined above may have a composition according to formula (Ia), where 5.85≦y≦6.15, more preferably 5.9≦y≦6.1, most preferably 5.95≦y≦6.05.

[0034] More specifically, the first group of solid materials defined above may have a composition according to formula (Ia), where 0.08≦x≦0.85, preferably 0.1≦x≦0.8, more preferably 0.12≦x≦0.65, most preferably 0.15≦x≦0.6, and 5.85≦y≦6.15, more preferably 5.9≦y≦6.1, most preferably 5.95≦y≦6.05.

[0035] The first group of particular solid materials defined above may have a composition according to formula (Ia), wherein M is Zr, X is Cl, 0.05≦x≦0.95, more particularly 0.08≦x≦0.85, preferably 0.1≦x≦0.8, more preferably 0.12≦x≦0.65, most preferably 0.15≦x≦0.6, and 5.8≦y≦6.2, more particularly 5.85≦y≦6.15, preferably 5.9≦y≦6.1, most preferably 5.95≦y≦6.05.

[0036] The solid material according to formula (Ia) (where M is Zr, X is Cl, x is <0.1, and y is as defined above for formula (Ia)) exhibits a crystalline phase in the P-3m1 space group, like the parent compound Li3YbCl6. 3+ Ions are Zr 4+ When substituted with ions (0.1≦x<0.3), a second crystalline phase with orthorhombic symmetry (Pnma space group) appears. For x≧0.3, said second crystalline phase with a different orthorhombic symmetry (Pnma space group) is predominantly present.

[0037] The second group of solid state materials according to the first aspect defined herein has a composition according to formula (I), where X is as defined above; and M is one or more of V, Nb, and Ta. In said second group of solid state materials, M is a pentavalent metal, so n is 2. Accordingly, said second group of solid state materials has a composition according to formula (Ib): Li 3-2x Yb 1-x M x X y (Ib) (In the formula, M is one or more selected from the group consisting of V, Nb, and Ta; X is one or more selected from the group consisting of halides and pseudohalides; 0.05 ≤ x ≤ 0.95; 5.8≦y≦6.2) The composition is as follows:

[0038] The second group of solid materials defined above may have a composition according to formula (Ib), where X is one or more halides selected from the group consisting of Cl, Br, and I. More specifically, the second group of solid materials defined above may have a composition according to formula (Ib), where X is Cl.

[0039] The second group of solid materials defined above may have a composition according to formula (Ib), where M is one or both of Nb and Ta. More specifically, the second group of solid materials defined above may have a composition according to formula (Ib), where M is one or both of Nb and Ta, and X is one or more halides selected from the group consisting of Cl, Br, and I, preferably Cl.

[0040] The second group of solid materials defined above may have a composition according to formula (Ib), where 0.08≦x≦0.85, preferably 0.1≦x≦0.8, more preferably 0.12≦x≦0.65, and most preferably 0.15≦x≦0.6.

[0041] The second group of solid materials defined above may have a composition according to formula (Ib), where 5.85≦y≦6.15, more preferably 5.9≦y≦6.1, most preferably 5.95≦y≦6.05.

[0042] More specifically, the second group of solid materials defined above may have a composition according to formula (Ib), where 0.08≦x≦0.85, preferably 0.1≦x≦0.8, more preferably 0.12≦x≦0.65, most preferably 0.15≦x≦0.6, and 5.85≦y≦6.15, preferably 5.9≦y≦6.1, most preferably 5.95≦y≦6.05.

[0043] The second group of solid materials defined above may have a composition according to formula (Ib), wherein M is Nb or Ta, X is Cl, and 0.05≦x≦0.95, more particularly 0.08≦x≦0.85, preferably 0.1≦x≦0.8, more preferably 0.12≦x≦0.65, and most preferably 0.15≦x≦0.6; and 5.8≦y≦6.2, more particularly 5.85≦y≦6.15, preferably 5.9≦y≦6.1, and most preferably 5.95≦y≦6.05.

[0044] The solid state material according to the first aspect defined herein may have an ionic conductivity of in each case 0.1 mS / cm or more, preferably 0.5 S / cm or more, more preferably 1 mS / cm or more, at a temperature of 25° C. The ionic conductivity is determined by electrochemical impedance spectroscopy in the usual manner known in the field of solid state battery materials development (see the Examples section below for details).

[0045] At the same time, the solid-state material according to the first aspect defined herein may have an almost negligible electronic conductivity. More specifically, the electronic conductivity may be at least three orders of magnitude lower than the ionic conductivity, preferably at least five orders of magnitude lower than the ionic conductivity. In certain cases, the solid-state material according to the first aspect defined herein may have an ionic conductivity of at least 10 -10 The electronic conductivity is determined by direct current (DC) polarization measurements at different voltages, using conventional methods known in the field of battery materials development.

[0046] Preferred solid materials according to the first aspect as defined herein are those that have one or more of the specific and preferred characteristics disclosed above.

[0047] According to a second aspect, there is provided a method for obtaining a solid material according to the first aspect defined above, said method comprising the following method steps: (a) precursor of (1) one or more compounds selected from the group consisting of halides and pseudohalides of Li; (2) one or more compounds selected from the group consisting of halides and pseudohalides of Yb; (3) one or more compounds selected from the group consisting of halides and pseudohalides of an element M selected from the group consisting of Ti, Zr, Hf, V, Nb, and Ta; providing wherein the molar ratios of Li, Yb, M, halide, and pseudohalide in the reaction mixture correspond to general formula (I): (b) reacting the precursors to obtain a solid material having a composition according to general formula (I).

[0048] In step a) of the method according to the second aspect defined above, a reaction mixture is provided comprising a precursor for the reaction product to be formed in step b), said precursor comprising (1) one or more compounds LiX; and (2) one or more compounds YbX; and (3) The following compounds MX4, in which M is selected from the group consisting of Ti, Zr and Hf; and - one or more compounds selected from the group consisting of: compounds MX5, in which M is selected from the group consisting of V, Nb and Ta; wherein, in each of precursors (1) to (3), independently of the other precursors, X is one or more selected from the group consisting of halides and pseudohalides; The molar ratios of Li, Yb, M and X correspond to general formula (I).

[0049] Preferably, the reaction mixture consists of precursors (1), (2) and (3) as defined above.

[0050] In some cases, in each of precursors (1) to (3), independently of the other precursors, X is one or more selected from the group consisting of Cl, Br, and I. Preferably, in each of precursors (1) to (3), X is the same, and preferably Cl.

[0051] In a method according to the second aspect defined above, precursor (3) is one or more compounds from the group consisting of compounds MX4, where M is selected from the group consisting of Ti, Zr and Hf, and X is as defined above. Such a method is suitable for preparing a solid material having a composition according to general formula (Ia) defined above.

[0052] Thus, suitable precursors of solid materials having a composition according to general formula (Ia) are (1) one or more compounds LiX; and (2) one or more compounds YbX; and (3) one or more compounds from the group consisting of compounds MX4, wherein M is selected from the group consisting of Ti, Zr and Hf, preferably Zr; wherein, in each of precursors (1) to (3), independently of the other precursors, X is one or more selected from the group consisting of halides and pseudohalides; The molar ratios of Li, Yb, M and X correspond to general formula (Ia).

[0053] Preferably, the reaction mixture consists of precursors (1), (2) and (3) as defined above.

[0054] In some cases, in each of precursors (1) to (3), independently of the other precursors, X is one or more selected from the group consisting of Cl, Br, and I. Preferably, in each of precursors (1) to (3), X is the same, and preferably Cl.

[0055] In one embodiment, in precursor (3), M is Zr.

[0056] Specifically, in each of precursors (1) to (3), independently of the other precursors, X is one or more selected from the group consisting of Cl, Br, and I, and in precursor (3), M is Zr. More specifically, in each of precursors (1) to (3), X is Cl, and in precursor (3), M is Zr.

[0057] In a method according to the second aspect defined above, precursor (3) is one or more compounds selected from the group consisting of compounds MX5, where M is selected from the group consisting of V, Nb and Ta, and X is as defined above. Such a method is suitable for preparing a solid material having a composition according to general formula (Ib) defined above.

[0058] Thus, suitable precursors of solid materials having a composition according to general formula (Ib) are (1) one or more compounds LiX; and (2) one or more compounds YbX; and (3) one or more compounds selected from the group consisting of compounds MX5, wherein M is selected from the group consisting of V, Nb, and Ta; wherein, in each of precursors (1) to (3), independently of the other precursors, X is one or more selected from the group consisting of halides and pseudohalides; The molar ratios of Li, Yb, M and X correspond to general formula (Ib).

[0059] Preferably, the reaction mixture consists of precursors (1), (2) and (3) as defined above.

[0060] In some cases, in each of precursors (1) to (3), independently of the other precursors, X is one or more selected from the group consisting of Cl, Br, and I. Preferably, in each of precursors (1) to (3), X is the same, and preferably Cl.

[0061] In some cases, in precursor (3), M is one or both of Nb and Ta.

[0062] In a specific case, in each of precursors (1) to (3), independently of the other precursors, X is one or more selected from the group consisting of Cl, Br, and I, and in precursor (3), M is Ta or Nb. More specifically, in each of precursors (1) to (3), X is Cl, and in precursor (3), M is Ta or Nb.

[0063] The process according to the second aspect defined above may be a thermochemical solid-state process or may be a solution-based process (solution-based synthesis).

[0064] The thermochemical solid-state process according to the second aspect defined above comprises the following steps: (a1) preparing or providing a solid reaction mixture comprising precursors (1), (2), and (3); (b1) heat treating the reaction mixture at a temperature ranging from 300°C to 650°C for a total time period ranging from 5 hours to 50 hours to form a reaction product, and cooling the reaction product to obtain a solid material having a composition according to general formula (I); Includes.

[0065] In step (a1) of the thermochemical solid-state process defined above, the solid reaction mixture can be obtained by mixing the precursors. Mixing the precursors can be carried out by grinding the precursors together. Grinding can be carried out using any suitable means.

[0066] The reaction mixture prepared or provided in step (a1) can be formed into pellets, which are heat-treated in step (b1), after which a solid material in the form of pellets or chunks is obtained, which can be ground into a powder for further processing.

[0067] In step (a1), it is useful that any handling operations are carried out under a protective gas atmosphere.

[0068] In step (b1) of the method according to the second aspect defined above, the reaction mixture may be reacted to result in a solid material having a composition according to general formula (I). In other words, in step (b1), the precursors in the reaction mixture react with each other to result in a solid material having a composition according to general formula (I).

[0069] The reaction mixture prepared in process step (a1) is heat-treated in process step (b1) to allow the reaction of the precursors, said reaction being considered to be a substantially solid-state reaction, i.e., occurring in the reaction mixture in the solid state.

[0070] The heat treatment can be carried out in a sealed vessel, which can be a sealed quartz tube or any other type of vessel that can withstand the temperatures of the heat treatment and does not react with any of the precursors, such as a vitreous carbon crucible or a tantalum crucible.

[0071] In step (b1), the reaction mixture may be heat treated at a temperature ranging from 300° C. to 650° C. for a total time ranging from 5 hours to 50 hours to form a reaction product. More specifically, in step (b1), the reaction mixture may be heat treated at a temperature ranging from 350° C. to 650° C. for a total time ranging from 5 hours to 15 hours. The heat treatment in step (b1) may be carried out under vacuum or under a protective gas atmosphere.

[0072] After the heat treatment time of step (b1) is completed, the formed reaction product is cooled to obtain a solid material having the composition according to general formula (I). The reaction product is preferably cooled at a rate of 1 to 10°C per minute.

[0073] The solution-based method according to the second aspect defined above comprises the following steps: (a2) Precursors (1), (2), and (3) were reacted with ether, HO, alcohol C n H 2n+1 OH (where 1≦n≦20), formic acid, acetic acid, dimethylformamide, N-methylformamide, pyridine, nitrile, N-methylpyrrolidinone, dimethyl sulfoxide, acetone, ethyl acetate, dimethoxyethane, 1,3-dioxolane, alkylene carbonate; (b2) removing the solvent from the liquid reaction mixture to obtain a solid residue, heat treating the solid residue at a temperature ranging from 100°C to 300°C for a total time period ranging from 4 hours to 24 hours to form a reaction product, and cooling the reaction product to obtain a solid material having a composition according to general formula (I); Includes.

[0074] In step (a2) of the solution-based method, the precursors (1), (2), and (3) are reacted with ether, HO, alcohol C n H 2n+1 A liquid reaction mixture is prepared by dissolving the compound in a solvent selected from the group consisting of OH (1≦n≦20), formic acid, acetic acid, dimethylformamide, N-methylformamide, pyridine, nitriles, dimethyl sulfoxide, acetone, ethyl acetate, dimethoxyethane, 1,3-dioxolane, N-methylpyrrolidinone, and alkylene carbonates. Mixtures of two or more solvents selected from the above group are also possible. Preferred solvents are ethers, alcohols with 1≦n≦6, and pyridine.

[0075] The liquid reaction mixture prepared in step (a2) of the solution-based method comprises ether, HO, alcohol C n H 2n+1The precursors (1), (2) and (3) are in the form of a solution of the precursors (1), (2) and (3) defined above in a solvent selected from the group consisting of OH (1≦n≦20), formic acid, acetic acid, dimethylformamide, N-methylformamide, pyridine, nitriles, dimethylsulfoxide, acetone, ethyl acetate, dimethoxyethane, 1,3-dioxolane, N-methylpyrrolidinone and alkylene carbonates. Mixtures of two or more solvents selected from the group are also possible. Preferred solvents are ethers, alcohols C with 1≦n≦6. n H 2n+1 OH, pyridine.

[0076] The combined content of precursors (1), (2) and (3) in the liquid reaction mixture prepared in step (a2) of the solution-based method is in the range of 1% to 80%, preferably 3% to 30%, based on the total mass of the liquid reaction mixture (the sum of the masses of all precursors and solvent).

[0077] The solution-based method does not involve mechanochemical milling (ie, reactive milling) of the precursors (1), (2) and (3) or of the mixture.

[0078] It is presently envisaged that solution-based synthesis according to the methods described herein provides for intimate mixing of precursors, potentially reducing the temperature and / or duration of the subsequent heat treatment in step (b2) of the solution-based method compared to the heat treatment applied in a purely thermochemical synthesis of the corresponding material.

[0079] In step (a2) of the solution-based method, any handling operations are preferably carried out under a protective gas atmosphere.

[0080] In step (b2) of the solution-based process, the liquid reaction mixture is converted to a solid material according to general formula (I) by removing the solvent to give a solid residue, followed by heat treatment (sintering) of the solid residue.

[0081] In step (b2) of the solution-based process, removal of the solvent is preferably achieved by reducing the pressure (vs. standard pressure of 101.325 kPa) on the solution under dynamic vacuum (continuous removal of solvent vapor from the reaction vessel) at a temperature ranging from 0°C to 100°C, preferably from 20°C to 40°C.

[0082] In step (b2) of the solution-based process, after removal of the solvent, the heat treatment of the resulting residue is preferably carried out in a closed vessel at a temperature ranging from 100°C to 300°C, even more preferably from 100°C to 250°C, most preferably from 100°C to 200°C, for a time period ranging from 1 to 12 hours, more preferably from 4 to 8 hours.

[0083] The heat treatment of step (b2) of the solution-based method is carried out under vacuum or under a protective gas atmosphere.

[0084] If necessary, the solid material obtained by the solution-based method according to the present invention as described above is ground into a powder.

[0085] Preferred methods according to the second aspect defined herein are those having one or more of the specific features disclosed above.

[0086] According to a third aspect, a solid material according to the first aspect as defined above or obtained by the method according to the second aspect as defined above, a positive electrode active material; A composite comprising:

[0087] In the context of this disclosure, an electrode of an electrochemical cell that generates a net positive charge upon discharge of the electrochemical cell is referred to as the positive electrode (cathode), and the component of the positive electrode that generates said net positive charge upon reduction of the positive electrode is referred to as the "positive electrode active material."

[0088] In the composite as defined above, the solid material according to the first aspect as defined above or the solid material obtained by the method according to the second aspect as defined above may contain Li +It functions as a solid electrolyte that is conductive to ions (lithium ions).

[0089] A preferred positive electrode active material has a V vs. Li / Li of 4 or more. + ("4V class" positive electrode active material), which allows for high battery voltages to be obtained. Several such positive electrode active materials are known in the art.

[0090] A preferred positive electrode active material is a compound represented by the general formula (II): Li 1+t [Co x Mn y Ni z M u ] 1-t O2(II) (In the formula, 0≦x≦1 0≦y≦1 0≦z≦1 0≦u≦0.15 When present, M is one or more elements selected from the group consisting of Al, Mg, Ba, B, and transition metals other than Ni, Co, and Mn; x+y+z>0 x+y+z+u=1 -0.05≦t≦0.2) The material is selected from the group consisting of materials having a composition according to

[0091] In certain active cathode materials according to Formula (II), M can be one of Al, Mg, Ti, Mo, Nb, W, and Zr. Exemplary active cathode materials of Formula (II) include Li 1+t [Ni 0.88 Co 0.08 Al 0.04 ] 1-t O2,Li 1+t [Ni 0.905 Co 0.0475 Al 0.0475 ] 1-t O2 and Li 1+t [Ni 0.91 Co 0.045 Al 0.045 ] 1-tO2 (where -0.05 ≤ t ≤ 0.2 in each case).

[0092] Suitable positive electrode active materials are, for example, oxides containing lithium and one or more members of the group consisting of nickel, cobalt, and manganese. These positive electrode active materials have the general formula (IIa): Li 1+t [Co x Mn y Ni z ] 1-t O2(IIa) (In the formula, 0≦x≦1 0≦y≦1 0≦z≦1 x+y+z=1 -0.05≦t≦0.2) The composition is as follows:

[0093] Preferably, the positive electrode active material according to general formula (IIa) is a mixed oxide of lithium and at least one of nickel and manganese, more preferably a mixed oxide of lithium, nickel and one or both members of the group consisting of cobalt and manganese.

[0094] An exemplary cathode active material according to Formula (IIa) is LiCoO2,Li 1+t [Ni 0.85 Co 0.10 Mn 0.05 ] 1-t O2,Li 1+t [Ni 0.87 Co 0.05 Mn 0.08 ] 1-t O2,Li 1+t [Ni 0.83 Co 0.12 Mn 0.05 ] 1-t O2 and Li 1+t [Ni 0.6 Co 0.2 Mn 0.2 ] 1-t O2(NCM622) and LiNi 0.5 Mn 1.5O4 (where -0.05≦t≦0.2 in each case).

[0095] An exemplary positive electrode active material that may be used in combination with the solid-state material according to the first aspect defined above is represented by the formula (IIb): Li 1+t A 1-t O2(IIb), (In the formula, A is nickel and mixed oxides with one or both members of the group consisting of cobalt and manganese, optionally one or more further transition metals not selected from the group consisting of nickel, cobalt and manganese, wherein said further transition metals are preferably selected from the group consisting of molybdenum, titanium, tungsten, zirconium, - containing one or more elements selected from the group consisting of aluminum, barium, boron and magnesium, wherein at least 50 mol % of the transition metals in A is nickel; t is a number ranging from -0.05 to 0.2) is a compound of

[0096] Suitable positive electrode active materials having a composition according to formula (IIb) are described in WO2020 / 249659A1.

[0097] An exemplary positive electrode active material of formula (IIb) that may be used in combination with the solid-state material according to the first aspect defined above is Li 1+t [Ni 0.85 Co 0.10 Mn 0.05 ] 1-t O2,Li 1+t [Ni 0.87 Co 0.05 Mn 0.08 ] 1-t O2,Li 1+t [Ni 0.83 Co 0.12 Mn 0.05 ] 1-t O2,Li1+t [Ni 0.6 Co 0.2 Mn 0.2 ] 1-t O2,Li 1+t [Ni 0.88 Co 0.08 Al 0.04 ] 1-t O2,Li 1+t [Ni 0.905 Co 0.0475 Al 0.0475 ] 1-t O2 and Li 1+t [Ni 0.91 Co 0.045 Al 0.045 ] 1-t O2 (where -0.05 ≤ t ≤ 0.2 in each case).

[0098] In the composite defined above, the cathode active material and the solid material according to the first aspect defined above can be blended with each other. More specifically, in the composite defined in the third aspect herein, the cathode active material and the solid material according to the first aspect defined above can be blended with each other and with one or more binders and / or one or more electronically conductive materials. Typical electronically conductive materials include or consist of elemental carbon, such as carbon black, graphite, and carbon nanofibers. Typical binders include poly(vinylidene fluoride) (PVDF), styrene butadiene rubber (SBR), polyisobutene, poly(ethylene vinyl acetate), poly(acrylonitrile butadiene), etc.

[0099] The composite as defined herein may be in the form of a coated particulate material, said coated particulate material comprising: C1) a plurality of core particles, each core particle comprising at least one positive electrode active material; C2) a coating disposed on the surface of the core particle, - Carbonate anion - and at least one solid material having a composition according to general formula (I) as defined above, Includes.

[0100] In the coated particulate material, the coating C2) is disposed on the surface of at least a portion of the core particles C1) present in the coated particulate material, preferably on the surface of more than 50% of the total number of core particles C1), more preferably on the surface of 75% or more of the total number of core particles C1), even more preferably on the surface of 90% or more of the total number of core particles C1), and even more preferably on the surface of 95% or more of the total number of core particles C1). For the purposes of the present disclosure, the portion of core particles C1) on which the coating C2) is disposed can be determined by electron microscopy performed on a representative sample of the coated particulate material.

[0101] In the coated particulate material ac, the coating C2) is disposed on at least a portion of the surface of the (individual) core particles C1), preferably on more than 50% of the total surface of the core particles C1), more preferably on 75% or more of the total surface of the core particles C1), and even more preferably on 90% or more of the total surface of the core particles C1). For the purposes of the present disclosure, the portion of the surface of the core particles C1) on which the coating C2) is disposed can be determined by electron microscopy performed on a (representative) sample of the (individual) coated particles of the coated particulate material or on a (representative) sample of the coated particulate material.

[0102] In the coated particulate material, the lithium present in the coating C2) is preferably present as part of a solid material having a composition according to general formula (I) above and lithium carbonate (Li2CO3). Preferably, the total amount of lithium present in the coating C2) is present as part of a solid material having a composition according to general formula (I) above and lithium carbonate (Li2CO3).

[0103] In the coated particulate material, the coating C2) can contain carbonate anions in a total amount of ≥ 0.12% or ≥ 0.15%, in each case relative to the total mass of the plurality of uncoated core particles C1). More specifically, the coating C2) can contain carbonate anions in a total amount ranging from 0.12% to 3.0%, preferably from 0.15% to 2.5%, more preferably from 0.15% to 2.0%, and even more preferably from 0.15% to 1.0%, relative to the total mass of the plurality of uncoated core particles C1). If the lithium carbonate content in the coating C2) is too high, the lithium ion conductivity may decrease.

[0104] Without wishing to be bound by any theory, it is currently believed that the carbonates present on the surface of the core particles C1) result from unavoidable impurities of the active cathode material, which are formed when the active cathode material is prepared or stored in the presence of traces of carbon dioxide and humidity, and / or in certain cases from the use of lithium carbonate as a precursor for the synthesis of the active cathode material, and / or from the decomposition of the organic solvent of the liquid reaction mixture used in preparing the coating particulate material (see below for details) in air or oxygen, and its reactivity with residual lithium on the particle surface of the active cathode material.

[0105] In the coated particulate materials described herein, at least a portion of the carbonate ions present in coating C2) may be present as part of an ionic compound, for example as part of a salt, wherein at least a portion of the carbonate ions present in coating C2), preferably the total amount of carbonate ions present in coating C2), are present as lithium carbonate.

[0106] For the purposes of the present disclosure, the amount of carbonate ions present in the coating C2) may be determined by acid titration combined with mass spectrometry, more preferably carried out on a representative sample of the coated particulate material, according to the method defined in the Examples section of WO2020 / 249659A1.

[0107] The thickness of the coating C2) may be in the range of 1 nm to 1 μm, preferably in the range of 1 nm to 50 nm.

[0108] In some cases, the coated particulate materials described herein are C1) a plurality of core particles, each core particle comprising at least one active cathode material, preferably at least one active cathode material having a composition according to general formula (II) defined above; C2) a coating disposed on the surface of the core particle, - carbonate anion, preferably lithium carbonate; and at least one solid material having a composition according to general formula (I) as defined above, preferably according to general formula (Ia) as defined above. coatings, including It comprises or consists of:

[0109] The method for preparing the coated particulate material defined above comprises the following steps: (i) preparing or providing a liquid reaction mixture, such as step (a2) of the solution-based method described above in the context of the second aspect; (ii) preparing or providing a plurality of core particles C1), each core particle comprising at least one positive electrode active material; (iii) contacting the core particles C1) and the liquid reaction mixture with each other; (iv) removing the solvent from the liquid reaction mixture to obtain a solid residue, and heat treating the solid residue at a temperature in the range of 100°C to 300°C for a total time in the range of 4 hours to 12 hours to obtain a coated particulate material as defined above; Includes.

[0110] The preparation of the liquid reaction mixture (step (i)) is carried out as disclosed above in the context of the solution-based method of the second aspect. Regarding preferred specific precursors for the preparation of the liquid reaction mixture, reference is made to the disclosure provided above in the context of the second aspect of the present disclosure. Regarding preferred specific solvents for preparing the liquid reaction mixture, reference is made to the disclosure provided above in the context of the solution-based method of the second aspect of the present disclosure.

[0111] Methods for preparing core particles C1) comprising (step (ii)), preferably consisting of, at least one active cathode material, are known in the art. Core particles C1) comprising or consisting of at least one active cathode material are commercially available. See above for specific preferred active cathode materials.

[0112] In step (iii) of the method for preparing the coated particulate material defined above, the core particles C1) and the liquid reaction mixture can be brought into contact with each other by any suitable technique, for example by mixing and / or spraying. For improved or complete contact, for example to complete the preparation of a mixture or gel, ultrasonic treatment can be used, preferably at a temperature ranging from 15°C to 30°C for a time ranging from 15 to 60 minutes.

[0113] In step (iv) of the process for preparing the coated particulate material defined above, removal of the solvent from the liquid reaction mixture (prepared in step (i)) is preferably achieved by applying reduced pressure (vs. standard pressure of 101.325 kPa) at a temperature in the range of from 0°C to 100°C, preferably from 20°C to 40°C.

[0114] In step (iv), heat treating the solid residue may comprise calcining the solid residue. The heat treatment in step (iv) may be carried out in the presence of carbon dioxide, oxygen, air, nitrogen, NO, or argon.

[0115] In step (iv), the solid residue may be comminuted prior to heat treatment.

[0116] It is understood that the method for preparing the coated particulate material defined above can be considered a combination of a solution-based synthesis (as described above in the context of the second aspect of the present disclosure) of a solid material having a composition according to general formula (I) and coating core particles C1) comprising a positive electrode active material with a coating C2) comprising the solid material having a composition according to general formula (I) obtained by solution-based synthesis. In other words, in the method for preparing the coated particulate material defined above, the solution-based synthesis (as described above in the context of the second aspect of the present disclosure) of a solid material having a composition according to general formula (I) is carried out in the presence of core particles C1) comprising a positive electrode active material in a liquid reaction mixture. Thus, the solution-based synthesis (as described above in the context of the second aspect of the present disclosure) of a solid material having a composition according to general formula (I) allows for the direct formation of such a solid material as part of the coating C2) on core particles C1) comprising a positive electrode active material.

[0117] The composite according to the third aspect defined above may be used to prepare a positive electrode (cathode) for an electrochemical cell.

[0118] The composite according to the third aspect defined above can be used in the positive electrode (cathode) of an electrochemical cell.

[0119] To have excellent electrochemical oxidation stability, the solid material (as defined above) according to the first aspect of the present disclosure has a V vs. Li / Li ratio of 4 or more, preferably 4.5 or more. + The solid electrolyte may be applied as a solid electrolyte in direct contact with a positive electrode active material having an oxidation-reduction potential of 0.01 to 0.025. When the positive electrode active material is discharged, an oxidation side reaction of the solid electrolyte does not substantially occur.

[0120] This is an important advantage since it may enable the application of an electrochemical cell construction in which the active cathode material is in direct contact with the solid electrolyte in the form of a solid material according to the first aspect defined above, so that a protective layer between the active cathode material and the solid electrolyte can be omitted, thus reducing the complexity of the electrochemical cell construction and its manufacturing method, and also omitting the additional ohmic resistance necessarily introduced by the protective layer.

[0121] Preferred conjugates according to the third aspect defined herein are those which have one or more of the particular and preferred characteristics disclosed above.

[0122] The solid material according to the first aspect defined above or the solid material obtained by the method according to the second aspect defined above can be used as a solid electrolyte for an electrochemical cell. The solid electrolyte can form a component of a solid structure for an electrochemical cell, the solid structure being selected from the group consisting of a positive electrode, a negative electrode, and a separator. Thus, the solid material according to the first aspect defined above or the solid material obtained by the method according to the second aspect defined above can be used alone or in combination with additional components to produce a solid structure for an electrochemical cell, such as a positive electrode, a negative electrode, or a separator. The substantial absence of undesired decomposition of the solid electrolyte can significantly improve the performance of the cell.

[0123] Thus, the present disclosure further provides the use of a solid material according to the first aspect defined above or obtained by the method according to the second aspect defined above as a solid electrolyte for an electrochemical cell. More particularly, the present disclosure further provides the use of a solid material according to the first aspect defined above or obtained by the method according to the second aspect defined above as a component of a solid structure for an electrochemical cell, said solid structure being selected from the group consisting of a positive electrode, a negative electrode and a separator.

[0124] In the context of this disclosure, an electrode in an electrochemical cell that develops a net negative charge during discharge is called the negative electrode, and an electrode in an electrochemical cell that develops a net positive charge during discharge is called the positive electrode. A separator electronically separates the positive and negative electrodes in an electrochemical cell.

[0125] The positive electrode of an all-solid-state electrochemical battery typically comprises a solid electrolyte as a further component in addition to the positive electrode active material. The negative electrode of an all-solid-state electrochemical battery typically comprises a solid electrolyte as a further component in addition to the negative electrode active material. The solid electrolyte may be a solid material according to the first aspect defined above or a solid material obtained by the method according to the second aspect defined above.

[0126] The morphology of the solid state structures of electrochemical cells, particularly all-solid-state lithium batteries, depends in particular on the exact morphology of the electrochemical cell being produced.

[0127] The present disclosure further provides a solid structure for an electrochemical cell, the solid structure being selected from the group consisting of a positive electrode, a negative electrode and a separator, and the solid electrolyte may be a solid material according to the first aspect defined above or a solid material obtained by the method according to the second aspect defined above. More specifically, the solid structure for an electrochemical cell may be a positive electrode comprising a composite according to the third aspect defined above.

[0128] The present disclosure further provides an electrochemical cell comprising a solid-state material according to the first aspect defined above or obtained by the method according to the second aspect defined above, in which the solid-state material according to the first aspect defined above or obtained by the method according to the second aspect defined above may form one or more solid structural components selected from the group consisting of a positive electrode, a negative electrode and a separator. More specifically, the present disclosure provides an electrochemical cell as defined above, in which in certain preferred cases the solid-state material according to the first aspect defined above or obtained by the method according to the second aspect defined above has a V vs. Li / Li of 4 or more, preferably 4.5 or more. +In accordance with the present invention, an electrochemical cell is provided in which the cathode active material is capable of direct contact with a cathode active material having a redox potential of 0.1 to 0.5 V.

[0129] The electrochemical cell defined above comprises the following components: α) at ​​least one negative electrode β) at least one positive electrode; γ) at least one separator; Including, Here, it can be a rechargeable electrochemical battery, at least one of the three components being a solid structure (selected from the group consisting of a positive electrode, a negative electrode and a separator) comprising the solid material according to the first aspect defined above or the solid material obtained by the method according to the second aspect defined above.

[0130] Suitable positive electrode active materials (electrochemically active positive electrode materials) and suitable negative electrode active materials (electrochemically active negative electrode materials) are known in the art. Exemplary positive electrode active materials are disclosed above in the context of the third aspect. In such electrochemical cells, the negative electrode α) can comprise graphitic carbon, metallic lithium, or a metal alloy containing lithium as the negative electrode active material. Such electrochemical cells can be alkali metal-containing batteries, particularly lithium-ion-containing batteries. In lithium-ion-containing batteries, Li + Charge transfer occurs through ions.

[0131] The electrochemical cell can have a discoid or prismatic shape. The electrochemical cell can include a housing that can be made of steel or aluminum.

[0132] Multiple electrochemical cells such as those described above can also be combined into an all-solid-state battery having both solid electrodes and a solid electrolyte. Further aspects of the present disclosure refer to batteries, more particularly alkali metal-ion batteries, and especially lithium-ion batteries, including at least one electrochemical cell such as those described above, such as two or more electrochemical cells such as those described above. Electrochemical cells such as those described above can be combined with one another in an alkali metal-ion battery, for example, in a series or parallel connection. A series connection is preferred.

[0133] The electrochemical cells or batteries described herein can be used to manufacture or operate stationary applications such as automobiles, computers, personal digital assistants, cell phones, watches, video cameras, digital cameras, thermometers, calculators, laptop BIOS, communication devices or remote car locks, and energy storage devices for power plants. A further aspect of the invention is a method for manufacturing or operating stationary applications such as automobiles, computers, personal digital assistants, cell phones, watches, video cameras, digital cameras, thermometers, calculators, laptop BIOS, communication devices, remote car locks, and energy storage devices for power plants by using at least one battery of the invention or at least one electrochemical cell of the invention.

[0134] A further aspect of the present disclosure is the use of an electrochemical cell as described above in an automobile, a bicycle operated by an electric motor, a robot, an aircraft (e.g., an unmanned aerial vehicle including a drone), a ship, or a stationary energy storage device.

[0135] The present disclosure further provides a device comprising at least one electrochemical cell of the present invention as described above. Preferred are mobile devices such as vehicles, e.g., automobiles, bicycles, aircraft, or water vehicles such as boats or ships. Other examples of mobile devices are portable devices, such as computers, particularly laptops, telephones, or power tools (e.g., in the construction sector), particularly drills, battery-powered screwdrivers, or battery-powered tackers.

[0136] The present invention is further illustrated by the following examples, which should not be construed as limiting the invention. [Example]

[0137] 1. Preparation of Solid Materials The solid material according to the first aspect of the invention, having a composition according to general formula (Ia), was prepared by the thermochemical solid-state method as described above, by mixing the following precursors in the proportions required to obtain the composition shown in Table 1: (1) LiCl (2) YbCl3 (3) ZrCl4 The reaction mixtures consisting of the following were prepared by homogeneously mixing precursors (1), (2), and (3) in an argon-filled glove box using a mortar and pestle (step a1). Each reaction mixture was reacted by heating at 450°C for 36 hours at 350°C or 650°C in a vacuum-sealed quartz tube (step b1). In each case, the resulting reaction product was cooled at a rate of 2°C / min to obtain a powdered solid material having the composition according to general formula (I) shown in Table 1.

[0138] 2.Structural analysis Powder X-ray diffraction (XRD) measurements of the solid materials obtained as described above were carried out at room temperature using a PANalytical Empyrean diffractometer with Cu-Kα radiation and a PIXcel two-dimensional detector. XRD patterns for phase identification were obtained in Debye-Scherrer geometry by sealing the samples in 0.3 mm glass capillaries under argon.

[0139] The solid material obtained as described above was polycrystalline and had little or no impurities, as can be deduced from the XRD pattern shown in FIG.

[0140] Figure 1 shows the Li SiO 2 nanoparticles obtained by heat treatment at 350°C over the range of x=0 to x=0.5 (see Table 1 below). 3-x Yb 1-x Zr xIt shows the X-ray diffraction (XRD) pattern of the Cl6 material. The XRD pattern of Li3YbCl6 (x = 0) corresponds to a hitherto unreported trigonal crystal structure (space group: P-3m1). For 0 < x < 0.1, the same structure is expected to be dominant. When more Yb 3+ ions are replaced by Zr 4+ ions (0.1 ≤ x < 0.3), a second crystal phase with orthorhombic symmetry (space group: Pnma) appears, and the mixture shows two-phase behavior. For x ≥ 0.3, the second crystal phase with orthorhombic symmetry (space group: Pnma) exists as the only phase.

[0141] 3. Ionic conductivity The ionic conductivity of the pellet-shaped Li 3-x Yb 1-x Zr x Cl6 (0 ≤ x ≤ 0.8) samples was determined by AC impedance technology using a battery configuration with ion-blocking Ti electrodes: Ti|Li 3-x Yb 1-x Zr x Cl6|Ti. The pellets were pressed at 374 MPa. The Nyquist plots were recorded in the frequency range of 1 MHz to 1 Hz using an MTZ-35 impedance analyzer (Bio-logic). The lithium ion conductivity at 25 °C and the Arrhenius equation σ T =A T exp(-E a / k B T) (where σ T is the ionic conductivity at temperature T, T is the temperature (in units of K), A T is the frequency factor, E a is the activation energy, and k B is the Boltzmann constant) were used to determine the activation energy as a function of temperature by a conventional method from the conductivity for all materials, and are shown in Table 1 below.

[0142]

Table 1

[0143] Table 1 shows that when some of the Yb is replaced with Zr, the ionic conductivity increases after passing through a plateau near 0.2 ≤ x ≤ 0.5. Further substitution of Yb with Zr does not result in any further increase in the ionic conductivity.

[0144] 4. Electrochemical Testing For electrochemical testing, LiCoO2 (a common cathode active material) and Li 3-x Yb 1-x Zr x The composite was prepared by mixing 10 mg of the prepared electrode composite with Cl6 (x = 0.3) in an 80:20 mass ratio. The working electrode was formed by spreading 10 mg of the prepared electrode composite on a layer of 50 mg of Li3PS4 pellets. A Li-In alloy was used as the counter electrode. The entire assembly was pressurized at 374 MPa in a poly(aryl-ether-ether-ketone) (PEEK) mold (diameter: 10 mm) with two Ti rods as current collectors before electrochemical testing. The resulting all-solid-state battery was composed of (LiCoO2Li 2.7 Yb 0.7 Zr 0.3 It has the composition: a mixture of Cl6 | Li3PS4 | Li-In alloy.

[0145] The cyclic voltammogram of the all-solid-state battery with the above-defined configuration is shown in Figure 2. The scan rate was 1 mV s -1 In the first scan, 3.5V vs Li / Li + A broad oxidation peak appears in this voltage range, and in the second scan, the peak is approximately 3.3 V vs Li / Li. + to about 4.7V vs Li / Li + During the first cycle, the interface between Li3PS4 and the working electrode is stabilized, probably due to the formation of a passivation layer, and the Li 3-x Yb 1-x Zr x It can be seen that Cl6 (x=0.3) exhibits substantial electrochemical oxidation stability in contact with the positive electrode active material LiCoO2.

[0146] Figure 3 shows the results of the (LiCoO2 and Li 2.7 Yb 0.7 Zr 0.3 Figure 1 shows the first (solid line) and second (dashed line) charge-discharge profiles (0.1 C) of the all-solid-state battery defined above with the following composition: Li3PS4|Li-In alloy (mixture of Li and Cl6)|Li3PS4|Li-In alloy.

[0147] The battery is 120mAhg -1 It shows a discharge capacity exceeding Li + No oxidative side reactions occurred before deintercalation of the ZnO. The second profile is not significantly different from the first profile, i.e., charge / discharge occurs almost reversibly.

[0148] Figure 4 shows the charge / discharge capacity as a function of cycle number at different C rates. The battery exhibits high coulombic efficiency and good capacity retention.

Claims

1. - A solid material having the general formula (I) Li 3-n*x Yb 1-x M x X y (I) (In the formula, 0.05≦x≦0.95; 5.8 ≤ y ≤ 6.2; n is the difference in valence between M and Yb; M is one or more selected from the group consisting of Ti, Zr, Hf, V, Nb, and Ta; X is one or more selected from the group consisting of halides and pseudohalides. A solid material having a composition according to and, A positive electrode active material, the positive electrode active material having the formula (II): Li １＋ｔ [Co ｘ Mn ｙ Ni ｚ M ｕ ] １－ｔ O ２ (II) (In the formula, 0≦x≦1 0≦y≦1 0≦z≦1 0≦u≦0.15, M, if present, is one or more elements selected from the group consisting of Al, Mg, Ba, B, and transition metals other than Ni, Co, and Mn; x + y + z > 0 x + y + z + u = 1 -0.05≦t≦0.2) a positive electrode active material comprising one or more compounds of Including, the solid material is present in the form of a coating on the positive electrode active material; Complex.

2. General formula (I) Li 3-n*x Yb 1-x M x X y (I) (In the formula, 0.05≦x≦0.95; 5.8 ≤ y ≤ 6.2; n is the difference in valence between M and Yb; M is one or more selected from the group consisting of Ti, Zr, Hf, V, Nb, and Ta; X is one or more selected from the group consisting of halides and pseudohalides; A solid material having a composition according to 1. A method for preparing a compound of formula (I), comprising: (a) precursors of: (1) one or more compounds selected from the group consisting of halides and pseudohalides of Li; (2) one or more compounds selected from the group consisting of halides and pseudohalides of Yb; (3) one or more compounds selected from the group consisting of halides and pseudohalides of an element M selected from the group consisting of Ti, Zr, Hf, V, Nb, and Ta; providing a wherein in the reaction mixture, the molar ratios of Li, Yb, M, halide and pseudohalide correspond to general formula (I): (b) reacting said precursors to obtain a solid material having a composition according to general formula (I), (a1) preparing or providing a solid reaction mixture comprising precursors (1), (2) and (3); (b1) heat treating the reaction mixture at a temperature ranging from 300°C to 650°C for a total time of at least 5 hours to form a reaction product, and cooling the reaction product to obtain a solid material having a composition according to general formula (I); A method comprising:

3. The precursor (1) one or more compounds LiX; (2) one or more compounds YbX ３ and, (3) one or more compounds MX ４ And, M is selected from the group consisting of Ti, Zr, and Hf; and / or X is selected from the group consisting of Cl, Br and I; The method of claim 2, wherein

4. The following steps (a2) Precursors (1), (2) and (3) are reacted with ethers, H ２ O, Alcohol C ｎ H ２ｎ＋１ preparing or providing a liquid reaction mixture by dissolving in a solvent selected from the group consisting of OH (where 1≦n≦20), formic acid, acetic acid, dimethylformamide, N-methylformamide, pyridine, nitriles, N-methylpyrrolidinone, dimethylsulfoxide, acetone, ethyl acetate, dimethoxyethane, 1,3-dioxolane, and alkylene carbonate; (b2) removing the solvent from the liquid reaction mixture to obtain a solid residue, heat treating the solid residue at a temperature ranging from 100°C to 300°C for a total time period ranging from 4 hours to 24 hours to form a reaction product, and cooling the reaction product to obtain a solid material having a composition according to general formula (I); The method of claim 2 or 3, comprising:

5. 10. A solid structure for an electrochemical cell, said solid structure being selected from the group consisting of a positive electrode, a negative electrode, and a separator, said solid structure for an electrochemical cell comprising the composite of claim 1.

6. An electrochemical cell comprising the composite of claim 1.

7. An electrochemical cell as described in claim 6, wherein the composite as described in claim 1 is a component of a solid structure as defined in claim 5.

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