Novel preparation method of LI-PSO products and corresponding products

Abstract

The present invention relates to a novel process for preparing a Li-PSO product, as well as to the product obtained by said process and its use, in particular as a solid electrolyte.

Description

[Technical field]

[0001] This application claims priority to European application No. 21315121.0 filed on July 06, 2021, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to a novel process for preparing a Li-PSO product, as well as to the product obtained by said process and its use, in particular as a solid electrolyte. [Background technology]

[0003] Lithium batteries are used to power portable electronics and electric vehicles due to their high energy and power density. Conventional lithium batteries utilize a liquid electrolyte consisting of lithium salts dissolved in an organic solvent. The organic solvent is flammable, which creates a safety issue in the aforementioned system. When lithium dendrites form and pass through the liquid electrolyte medium, they can cause short circuits and generate heat, which can lead to accidents that can result in serious injuries.

[0004] The non-flammable inorganic solid electrolyte provides a solution to the safety concerns, and its mechanical stability helps inhibit lithium dendrite formation, prevent self-discharge and heating problems, and extend the battery life.

[0005] Solid sulfide electrolytes are advantageous for lithium battery applications due to their high ionic conductivity and mechanical properties. These electrolytes can be pelletized and attached to the electrode materials by cold pressing, which eliminates the need for high temperature assembly steps. Eliminating the high temperature sintering step removes one of the problems for using lithium metal anodes in lithium batteries.

[0006] Therefore, new solid sulfide electrolytes are needed.

[0007] Li7P3S 11has very high Li + conductivity (1.4×10 -3 S cm -1 ) at 25 °C after cold pressing, which is a Li-P-S product (Y. Seino, T. Ota, K. Takada, A. Hayashi, M. Tatsumisago, A sulphide lithium super ion conductor is superior to liquid ion conductors for use in rechargeable batteries, Energy Environ. Sci. 7 (2014) 627-631; see

[16] ). However, it has the problem of low chemical and electrochemical stability. To avoid these drawbacks, several attempts have been made to enhance its stability by introducing O 2- ions into its structure [9-12, 15]. Conventionally, the glass-ceramic Li7P3S 11 [7] is synthesized by reacting P2S5 with Li2S, but the latter is quite expensive. The oxysulfide derivatives of Li7P3S 11 are generally synthesized by adding moisture-stable Li2O, P2O5, or Li3PO4 to the conventional precursor mixture (Li2S-P2S5) that is susceptible to the influence of moisture. Although the final oxysulfide product is more chemically and electrochemically stable [9-12, 15], due to Li2S and P2S5, which are reagents that are not chemically stable in the ambient atmosphere and are susceptible to the influence of moisture, the synthesis still needs to be carried out in an inert atmosphere, and the problem of high cost remains for scale-up synthesis.

Summary of the Invention

[0008] An object of the present invention is to provide a novel solid electrolyte containing particularly Li7P3S 11-x / 2 O x / 2 (0 < x ≤ 1).

[0009] Another object of the present invention is to provide a method for preparing Li7P3S 11-x / 2 O x / 2To provide a novel method for preparing Li-P-S-O products such as (0 < x ≤ 1).

[0010] Another object of the present invention is to prepare Li7P3S without the need to work in a protected atmosphere throughout the process 11-x / 2 O x / 2 To provide a novel method for preparing Li-P-S-O products such as (0 < x ≤ 1).

[0011] Accordingly, the present invention relates to a method for manufacturing Li-P-S-O products, the method comprising at least the following steps: (a) mixing at least Li4P2S6, sulfur, an oxygen-containing reagent selected from Li2CO3, Li2O, or a mixture thereof, and optionally Li2S to obtain a first mixture; (b) heating the first mixture in an inert atmosphere, under vacuum, or under a H2S stream for a time and at a temperature sufficient to produce the Li-P-S-O product; and (c) cooling the Li-P-S-O product and optionally pulverizing it. It includes.

[0012] Such a process is a new synthetic route for synthesizing a solid acid sulfide electrolyte corresponding to the formula Li7P3S 11-x / 2 O x / 2 For example, but not limited to, the 70Li2S - 27P2S5 - 3P2O5 (or Li7P3S 10.25 O 0.75 ) electrolyte exhibits an ionic conductivity of 2.61×10 -3 S·cm -1 , which is superior compared to pure Li7P3S -3 S·cm -1 exhibiting an ionic conductivity of 1.35×10 11

[17] .

[0013] Unlike existing reaction routes that require the use of Li2S and P2S5, which are not chemically stable in the ambient atmosphere, as reagents, this process is for Li-P-S-O compounds (i.e., the aforementioned Li7P3S11-x / 2 O x / 2 The Li-PS compound (i.e. Li4P2S6) is used as a reagent to synthesize Li-PS. The advantage of this particular reaction is that the traditional reagents Li2S and P2S5 need to be stored in a protective atmosphere such as Ar or N, whereas Li7P3S 11-x / 2 O x / 2 This increases the feasibility of using Li4P2S6 as a stored material that is simply placed in a dry room prior to synthesis of . Another advantage is that Li2CO3 (or Li2O), an affordable moisture-stable reagent, is used.

[0014] definition Throughout this specification, unless the context requires otherwise, the terms "comprise" or "include" or variations such as "comprises," "including," "includes," "comprising" and the like will be understood to imply the inclusion of a stated element or method step or group of elements or method steps, but not the exclusion of any other element or method step or group of elements or method steps. According to a preferred embodiment, the terms "comprise" and "comprises" and variations thereof mean "consisting only of."

[0015] As used herein, the singular forms "a", "an" and "the" include plural embodiments unless the context clearly indicates otherwise. The term "and / or" includes the meaning "and", "or" and also all other possible combinations of the elements associated with this term.

[0016] The term "~" should be understood to be inclusive.

[0017] Ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. Such a range format is used merely for convenience and brevity and is to be interpreted flexibly as encompassing not only the numerical values explicitly recited as the limits of the range but also all the individual numerical values or sub-ranges subsumed within that range as if each numerical value and sub-range were explicitly recited. For example, a temperature range of about 120°C to about 150°C is to be interpreted as encompassing not only the explicitly recited limits of about 120°C to about 150°C but also sub-ranges such as 125°C to 145°C, 130°C to 150°C, etc., as well as individual amounts within the specified range such as, for example, 122.2°C, 140.6°C, and 141.3°C. **DETAILED DESCRIPTION OF THE INVENTION**

[0018] Accordingly, the method of the present invention provides a Li-P-S-O product, i.e., a product containing lithium (Li), phosphorus (P), sulfur (S), and oxygen (O).

[0019] According to one embodiment, the Li-P-S-O product is selected from the group consisting of Li7P3S 11-x / 2 O x / 2 , Li3PS 4-x / 2 O x / 2 , and Li7PS 6-5x / 2 O 5x / 2 (0 < x ≤ 1).

[0020] More preferably, the Li-P-S-O product is Li7P3S 11-x / 2 O x / 2 .

[0021] Without being bound by any theory, the reaction suitable for obtaining the Li-P-S-O product can be written as follows (0 < x ≤ 1): · 3Li4P2S6 + 3S + (1 - x)Li2S + xLi2CO3 = 2Li7P3S 11-x / 2 O x / 2 + xCO2 · 3Li4P2S6 + 3S + (1 - x)Li2S + xLi2O = 2Li7P3S 11-x / 2O x / 2 · Li4P2S6+S+(1-x)Li2S+xLi2CO3=2Li3PS 4-x / 2 O X / 2 +xCO2 · Li4P2S6+S+(1-x)Li2S+xLi2O=2Li3PS 4-x / 2 O x / 2 · 2Li4P2S6+2S+(10-10x)Li2S+10xLi2CO3=4Li7PS 6-5x / 2 O 5x / 2 +10xCO2 · 2Li4P2S6+2S+(10-10x)Li2S+10xLi2O=4Li7PS 6-5x / 2 O 5x / 2

[0022] As mentioned above, step (a) of the method according to the invention is to prepare a first mixture from Li4P2S6, sulfur, an oxygen-containing reagent selected from Li2CO3, Li2O, or a mixture thereof, and optionally Li2S.

[0023] In some embodiments, the oxygen-containing reagent comprises Li2O. In some other embodiments, the oxygen-containing reagent comprises Li2O and the first mixture does not comprise Li2S. In some embodiments, the first mixture consists of Li4P2S6, sulfur, and Li2O.

[0024] In some embodiments, the oxygen-containing reagent comprises Li2CO3. In some other embodiments, the sulfur-containing reagent comprises Li2CO3 and the first mixture does not comprise Li2S. Excellent results have been obtained with a first mixture consisting of Li4P2S6, sulfur, and Li2CO3.

[0025] Such step (a) is carried out by implementing conventional means well known to those skilled in the art.

[0026] Preferably, step (a) consists of a chemomechanical or mechanochemical reaction.

[0027] Thereafter, according to step (b), the mixture is heated in an inert atmosphere, under vacuum or under flowing H2S, for a period of time and at a temperature sufficient to produce the Li-PSO product.

[0028] As mentioned above, step (b) can be carried out in an inert atmosphere or under vacuum. Step (b) can also include an additional sulfur source when the step is carried out under flowing H2S.

[0029] Such a heating step is carried out by conventional means well known to those skilled in the art, for example using a vacuum-sealed quartz tube, a batch furnace, or a rotary furnace that can be operated under a flow of argon, nitrogen, or H2S.

[0030] According to one embodiment, the temperature in step (b) is comprised between 150°C and 600°C, preferably between 180°C and 300°C.

[0031] According to one embodiment, the heating in step (b) is carried out for a time comprised between 0.1 h and 200 h, for example between 0.5 h and 100 h.

[0032] Step (c) consists of cooling the product obtained after step (b). Preferably, the product is cooled until it reaches room temperature. Such a cooling step is carried out by implementing conventional means well known to those skilled in the art, for example by lowering the furnace to room temperature at a rate of 5° C. / min.

[0033] In particular, the cooling is carried out under natural cooling for a time sufficient to obtain a cooled product having a temperature of about room temperature, which in the present invention is defined as about 25°C ± 2°C.

[0034] The method of the invention may also include an additional step of pulverization, which is carried out after the cooling step, by implementing conventional means well known to those skilled in the art, for example by grinding the sample in a mortar or by applying a low-energy deagglomeration step.

[0035] Subsequently, after step (c), Li-P-S-O is recovered by any means well-known to those skilled in the art, such as sieving the powder.

[0036] According to one embodiment, the Li4P2S6 added in step (a) is obtained from the reaction between Li2S and P2S5. Such reactions are well-described in the prior art and are well-known to those skilled in the art, such as high-temperature solid-state reactions as described in Journal of Solid State Chemistry, 43(1982), pp. 151-162.

[0037] The present invention also relates to Li-P-S-O products obtained by the method defined above.

[0038] As described above, the Li-P-S-O product is Li7P3S 11-x / 2 O x / 2 , Li3PS 4-x / 2 O x / 2 and Li7PS 6-5x / 2 O 5x / 2 (0 < x ≤ 1). Therefore, preferably, the present invention relates to Li7P3S 11-x / 2 O x / 2 obtained by the method defined above.

[0039] By implementing the method of the present invention, compared with the space group and lattice constants of Li-P-S-O products obtained by prior art methods, a specific Li-P-S-O product of the formula Li7P3S 11-x / 2 O x / 2 having the same space group (P-1) but different lattice constants is obtained.

[0040] Therefore, the present invention also relates to Li-P-S-O products of the formula Li7P3S 11-x / 2 O x / 2 having a crystal structure (space group P-1) measured by X-ray diffraction and a volume V (V / z) per formula unit included between 405 and 415 cubic angstroms at room temperature.

[0041] The present invention relates to a compound having the formula Li7P3S, which has a crystal structure (space group P-1) and a volume per formula unit V (V / z) contained within 405-415 cubic angstroms at room temperature, as determined by X-ray diffraction. 10.5 O 0.5 This also applies to Li-PSO products with (x=1).

[0042] X-ray diffraction (XRD) measurements were performed using Bragg-Brentano geometry with Cu (K-alpha1, K-alpha2) radiation in, for example, a D8 Bruker diffractometer. Preferred measurement conditions were 15 seconds per 0.03 degree step.

[0043] The volume per formula unit, V, is determined using the cell parameters taken at standard atmospheric pressure (101325 Pa) of the powder sample.

[0044] The volume per formula unit, V, is the lattice volume, V', divided by the number of formula units, Z, in the cell, where Z is 2 (Solid State Ionics, 178 (2007), pp. 1163-1167).

[0045] As is well known, V' is derived from the cell (lattice) parameters (a, b, c, α, β, γ). V'=abcsqrt(1+2cosα.cosβ.cosγ-cos 2 α-cos 2 β-cos 2 γ) (a, b, and c are the edge lengths (in angstroms (Å)) and α, β, and γ are the angles between them (in degrees).

[0046] According to one embodiment, the compound of the formula Li7P3S 11-x / 2 O x / 2 The Li-PSO products may also contain an amorphous phase.

[0047] Preferably, the compound according to the invention has the formula Li7P3S 11-x / 2 O x / 2The Li-PSO products have lattice parameters of the crystal structure, as determined by X-ray diffraction, between these values: a=12.35~12.50Å(by Le Bail method) b=6.01~6.05Å (by Le Bail method) c=12.43~12.53Å (by Le Bail method)

[0048] According to one embodiment, the compound of the formula Li7P3S 11-x / 2 O x / 2 The Li-PSO product has a crystal structure whose lattice constants, as determined by X-ray diffraction, lie between the following values: α=102.44°~103.14°Å(by Le Bail method) · β=112.88°~113.33° (by Le Bail method) · γ=74.47°~74.71° (by Le Bail method)

[0049] The present invention also relates to the use of the Li-PSO product defined above, alone or in combination with any crystalline or amorphous conductive Li material, as a solid electrolyte.

[0050] Preferably, the present invention relates to a compound of formula Li7P3S as defined above. 11-x / 2 O x / 2 and in particular the Li-PSO product having a crystal structure (space group P-1) and a volume per formula unit V (V / z) contained at room temperature between 405 and 415 cubic Angstroms, as determined by X-ray diffraction, alone as a solid electrolyte.

[0051] In this case, the solid electrolyte comprises at least one of the formula Li7P3S defined above. 11-x / 2 O x / 2 and optionally another solid electrolyte, such as lithium argyrodite, lithium thiophosphate, such as glass or glass ceramic Li3PS4, Li7P3S 11 , and lithium conducting oxides, such as the lithium-filled garnet Li7La3Zr2O12 (LLZO) and sulfides.

[0052] According to one embodiment, the Li-PSO product can be used in combination with any crystalline or amorphous conductive Li material, such as β-Li3PS4 or glassy Li3PS4.

[0053] The solid electrolyte may also optionally include a polymer, such as styrene butadiene rubber, an organic or inorganic stabilizer, or dispersant, such as SiO2.

[0054] The present invention also relates to a solid electrolyte comprising at least one Li-PSO product as defined above.

[0055] Preferably, the solid electrolyte according to the invention has the formula Li7P3S as defined above. 11-x / 2 O x / 2 in particular, a Li-PSO product having a crystal structure (space group P-1) and a volume per formula unit V (V / z) contained at room temperature between 405 and 415 cubic Angstroms, as determined by X-ray diffraction.

[0056] The present invention relates to a compound having at least the formula Li7P3S 11-x / 2 O x / 2 The present invention also relates to an electrochemical device comprising a solid electrolyte comprising a Li-PSO product of the present invention, in particular a Li-PSO product having a crystal structure (space group P-1) and a volume per formula unit V (V / z) comprised at room temperature of 405 to 415 cubic Angstroms, as determined by X-ray diffraction.

[0057] Preferably, in an electrochemical device, particularly a rechargeable electrochemical device, the solid electrolyte is a solid structural component for the electrochemical device selected from the group consisting of the cathode, the anode and the separator.

[0058] In this specification, preferably, the solid electrolyte is a component of a solid structure for an electrochemical device, where the solid structure is selected from the group consisting of a cathode, an anode, and a separator. Thus, the Li-P-S-O product according to the present invention can be used alone or in combination with additional components for manufacturing a solid structure for an electrochemical device, such as a cathode, an anode, or a separator.

[0059] The electrode at which a net negative charge is generated during discharge is called the anode, and the electrode at which a net positive charge is generated during discharge is called the cathode. The separator electrically separates the cathode and the anode from each other in an electrochemical device.

[0060] Suitable electrochemically active cathode materials and suitable electrochemically active anode materials are well known in the art. In the electrochemical device according to the present invention, the anode preferably contains graphite carbon, metallic lithium, Si, silicon compounds such as SiO x , lithium titanates such as Li4Ti5O 12 , or metal alloys containing lithium as an anode active material such as Sn.

[0061] In the electrochemical device according to the present invention, the cathode preferably contains a metal chalcogenide of the formula LiMQ2 (where M is at least one metal selected from transition metals such as Co, Ni, Fe, Mn, Cr, and V, and Q is a chalcogen such as O or S). Among these, it is preferable to use a lithium-based composite metal oxide of the formula LiMO2 (where M is the same as defined above). Preferred examples thereof include LiCoO2, LiNiO2, LiNixCo 1-x O2 (0 < x < 1), spinel-structured LiMn2O4, and LiMn 1.5 Ni 0.5 O4. Another preferred example is a compound of the formula LiNi x Mn y Co z O2 (x + y + z = 1, referred to as NMC), for example, LiNi1 / 3 Mn 1 / 3 Co 1 / 3 O2, LiNi 0.6 Mn 0.2 Co 0.2 O2 lithium-nickel-manganese-cobalt metal oxides and the formula LiNi x Co y Al z O2 (x+y+z=1, called NCA), e.g. LiNi 0.8 Co 0.15 Al 0.05 The cathode may include a lithium-nickel-cobalt-aluminum-based metal oxide of O2. The cathode may include a lithiated or partially lithiated transition metal oxyanion-based material such as LiFePO4.

[0062] For example, the electrochemical device has a cylindrical-like shape or a prismatic shape.The electrochemical device can include a housing, which can be made of steel or aluminum or a multi-layer film polymer / metal foil.

[0063] A further aspect of the present invention refers to a battery, more preferably an alkali metal battery, in particular a lithium battery comprising at least one, e.g. two or more, inventive electrochemical devices. The electrochemical devices can be combined, e.g. in series or parallel connection, with one another in the inventive alkali metal battery.

[0064] The present invention relates to a battery, preferably at least a Li-PSO product obtained by the method of the present invention, or a lithium-ion battery having the formula Li7P3S, having a crystal structure (space group P-1) and a volume per formula unit V (V / z) contained at room temperature between 405 and 415 cubic angstroms, as determined by X-ray diffraction. 11-x / 2 O x / 2 It also relates to lithium batteries, including those in the above-mentioned products.

[0065] The battery in which the Li-PSO product of the present invention is used can be a lithium ion or lithium metal battery.

[0066] Typically, a lithium solid-state battery includes a positive electrode active material layer containing a positive electrode active material, a negative electrode active material layer containing a negative electrode active material, and a solid electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer includes a solid electrolyte as defined above.

[0067] The cathode of an all-solid-state electrochemical device typically comprises a solid electrolyte as a further component in addition to the cathode active material, and the anode of an all-solid-state electrochemical device typically also comprises a solid electrolyte as a further component in addition to the anode active material.

[0068] The morphology of the solid-state structure for an electrochemical device, in particular an all-solid-state lithium battery, depends in particular on the morphology of the electrochemical device itself to be produced. The present invention further provides a solid-state structure for an electrochemical device selected from the group consisting of a cathode, an anode and a separator, the solid-state structure for an electrochemical device comprising a Li-PSO product according to the present invention.

[0069] Multiple electrochemical cells can be combined into an all-solid-state battery having both solid electrodes and a solid electrolyte.

[0070] The present invention also relates to an electrode comprising at least a Li-PSO product obtainable by the method of the present invention.

[0071] The Li-PSO products disclosed above can be used to prepare electrodes. The electrodes can be positive or negative electrodes.

[0072] The electrodes typically include at least a metal substrate; a layer of composition (C) in contact with the metal substrate, (i) the Li-PSO products disclosed above; (ii) at least one electroactive compound (EAC); (iii) optionally, at least one material that conducts Li-ions other than the Li-PSO product of the present invention; (iv) Optionally, at least one conductive material (ECM); (v) Optionally, a lithium salt (LIS); (vi) Optionally, at least one polymeric binder material (P); A layer of a composition (C) comprising is included.

[0073] Preferably, the electrode according to the present invention is of the Li-P-S-O product of the formula Li7P3S 11-x / 2 O x / 2 and includes a Li-P-S-O product having a crystal structure (space group P-1) measured by X-ray diffraction and a volume V (V / z) per formula unit included in the range of 405-415 cubic angstroms at room temperature.

[0074] An electroactive compound (EAC) means a compound that can incorporate or insert lithium ions into its structure and release them during the charging and discharging stages of an electrochemical device. The EAC can be a compound that can insert and desorb lithium ions into its structure. For a positive electrode, the EAC can be a complex metal chalcogenide of the formula LiMeQ2 (where - Me is at least one metal selected from the group consisting of Co, Ni, Fe, Mn, Cr, Al and V; - Q is a chalcogen such as O or S) can be.

[0075] More specifically, the EAC can be of the formula LiMeO2. Preferred examples of the EAC include LiCoO2, LiNiO2, LiMnO2, LiNi x Co 1-x O2 (0 <x <1), LiNi x Co y Mn z O2 (0 <x, y, z <1 and x + y + z = 1), for example LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O2, LiNi 0,6 Mn 0,2 Co 0,2 O2, LiNi0,8 Mn 0,1 Co 0,1 O2, Li(Ni x Co y Al z )O2(x+y+z=1) and spinel structured LiMn2O4 and Li(Ni 0.5 Mn 1.5 )O4 is one example.

[0076] EAC is the formula M1M2(JO4) f E 1-f (In the formula, - M1 is lithium, which may be partially replaced by another alkali metal, which is less than 20% of M1; - M2 is a transition metal with an oxidation level of +2 selected from Fe, Co, Mn, Ni or mixtures thereof, which may be partially replaced by one or more additional metals with an oxidation level of +1 to +5, inclusive, and which is less than 35% of the M2 metal; - JO4 is any oxyanion where J is P, S, V, Si, Nb, Mo or any combination thereof; - E is a fluoride, hydroxide or chloride anion; - f is the mole fraction of JO4 oxyanions, typically between 0.75 and 1) The electroactive material may be a lithiated or partially lithiated transition metal oxyanion based material.

[0077] M1M2(JO4) as defined above f E 1-f The electroactive material is preferably phosphate-based. It may exhibit an ordered structure or a modified olivine structure.

[0078] For the positive electrode, the EAC may be sulfur or Li2S.

[0079] For the positive electrode, the EAC may also be a conversion type material such as FeS2, or FeF2, or FeF3.

[0080] For the negative electrode, the EAC may be selected from the group consisting of graphitic carbons capable of intercalating lithium. Further details regarding this type of EAC may be found in Carbon 2000, 38, 1031-1041. This type of EAC typically exists in the form of powders, flakes, fibers or spheres (e.g., mesocarbon microbeads).

[0081] EAC can be any of a variety of materials, including lithium metal; lithium alloy compositions (such as those described in U.S. Pat. No. 6,203,944 and WO 00 / 03444); generally of the formula Li4Ti5O 12 Lithium titanates, represented by the formula Li (these compounds are generally considered "zero strain" insertion materials that exhibit a low level of physical expansion upon incorporation of mobile ions, i.e., Li+); lithium-silicon alloys, commonly known as lithium silicides, with high Li / Si ratios, particularly those of the formula Li 4.4 Lithium silicide of formula Si; and Li 4.4 It can also be a lithium-germanium alloy containing a crystalline phase of Ge. The EAC can also be a composite material based on silicon and / or silicon oxide-loaded carbonaceous materials, especially graphitic carbon / silicon and graphite / silicon oxide, where the graphitic carbon is composed of one or several carbons capable of intercalating lithium.

[0082] The ECM is typically selected from the group consisting of conductive carbonaceous materials and metal powders or fibers. The conductive carbonaceous materials may be selected from the group consisting of, for example, carbon black, carbon nanotubes, graphite, graphene, and graphite fibers, and combinations thereof. Examples of carbon black include ketjen black and acetylene black. Metal powders or fibers include nickel and aluminum powders or fibers.

[0083] The lithium salt (LIS) may be selected from the group consisting of LiPF6, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, LiB(C2O4)2, LiAsF6, LiClO4, LiBF4, LiAlO4, LiNO3, LiCF3SO3, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiC(SO2CF3)3, LiN(SO3CF3)2, LiC4F9SO3, LiCF3SO3, LiAlCl4, LiSbF6, LiF, LiBr, LiCl, LiOH, and lithium 2-trifluoromethyl-4,5-dicyanoimidazole.

[0084] The function of the polymeric binder (P) is to bind the components of the composition. The polymeric binder is usually inert. It should also preferably be chemically stable and facilitate electronic and ionic transport. Polymeric binders are well known in the art. Non-limiting examples of polymeric binders include vinylidene fluoride (VDF)-based (co)polymers, styrene-butadiene rubber (SBR), styrene-ethylene-butylene-styrene (SEBS), carboxymethylcellulose (CMC), polyamideimide (PAI), poly(tetrafluoroethylene) (PTFE) and poly(acrylonitrile) (PAN) (co)polymers, among others.

[0085] The proportion of the Li-PSO product of the present invention in the composition may be 0.1% to 80% by weight, based on the total weight of the composition. In particular, this proportion may be 1.0% to 60% by weight, more particularly 5% to 30% by weight. The thickness of the electrode is not particularly limited and should be adjusted with respect to the energy and power required in the application. For example, the thickness of the electrode may be 0.01 mm to 1,000 mm.

[0086] The present invention also relates to a separator comprising at least a Li-PSO product obtainable by the method of the present invention.

[0087] The Li-PSO product according to the invention can also be used to prepare a separator. A separator is an ion-permeable membrane that is placed between the anode and cathode of a battery. Its function is to allow lithium ions to pass through while blocking electrons and ensuring physical separation between the electrodes.

[0088] The separator of the present invention typically comprises at least - the Li-PSO product disclosed above; - optionally at least one polymeric binding material (P), optionally at least one metal salt, in particular a lithium salt, optionally at least one plasticizer; Includes.

[0089] Preferably, the separator according to the invention has the formula Li7P3S as defined above. 11-x / 2 O x / 2 in particular, a Li-PSO product having a crystal structure (space group P-1) and a volume per formula unit V (V / z) contained at room temperature between 405 and 415 cubic Angstroms, as determined by X-ray diffraction.

[0090] The electrodes and separators can be prepared using methods well known to those skilled in the art, which typically involve mixing the components in a suitable solvent and removing the solvent. For example, the electrodes can be prepared using the following steps: - applying a slurry comprising the components of the composition and at least one solvent onto a metal substrate; - Removing the solvent It can be prepared by a process comprising:

[0091] Common techniques known to those skilled in the art are: coating and calendaring, dry and wet extrusion, 3D printing, sintering of porous foams followed by impregnation. Common preparation techniques for electrodes and separators are provided in Journal of Power Sources, 2018 382, ​​160-175.

[0092] Electrochemical devices, particularly batteries such as the solid-state batteries described herein, can be used to manufacture or operate stationary applications such as automobiles, computers, personal digital assistants, cell phones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment or remote car locks, and energy storage devices for power plants.

[0093] Electrochemical devices, especially batteries such as the solid-state batteries described herein, can be used in, among others, motorized vehicles, bicycles driven by electric motors, robots, aircraft (e.g. unmanned aerial vehicles such as drones), ships or stationary energy storage. Mobile devices such as vehicles, for example automobiles, bicycles, aircraft or water vehicles such as boats or ships, are preferred. Other examples of mobile devices are those that are portable, such as computers, especially laptops, telephones or power tools, for example from the construction sector, especially drills, battery-powered screwdrivers or battery-powered nailers.

[0094] To the extent that the disclosures of any patents, patent applications, and publications incorporated herein by reference conflict with the statements of this application to the extent that any term may be unclear, the statements of this application shall control. [Brief description of the drawings]

[0095] [Figure 1] A comparison of the simulated pattern of Li4P2S6 [1] and the XRD pattern of the synthesized Li4P2S6 (Example 1). [Diagram 2] 1 is a comparison of Raman spectra of synthesized Li4P2S6 (Example 1), a ball milled product synthesized using Li2CO3 as one of the precursors (Example 2), crystalline Li7P3S11-x / 2Ox / 2 formed by annealing of Example 2 (Example 3), and crystalline Li7P3S11 synthesized from conventional reagents Li2S and P2S5 (Example 4). [Diagram 3]31P nuclear magnetic resonance (NMR) magic angle spinning (MAS) spectra of the synthesized Li4P2S6 (Example 1), the ball-milled product synthesized using Li2CO3 as one of the precursors (Example 2), the crystalline Li7P3S11-x / 2Ox / 2 formed by annealing of Example 2 (Example 3), and the crystalline Li7P3S11 synthesized from the conventional reagents Li2S and P2S5 (Example 4). The characteristic chemical shift intervals of the different structural sites (P2O7 4-, PO3S3-, PS4 3-, P2S7 4-, and P2S6 4-) are marked and labeled in different shades of grey. [Figure 4] Comparison of XRD patterns of crystalline Li7P3S11-x / 2Ox / 2 synthesized using Li2CO3 as one of the precursors (Example 3), crystalline Li7P3S11 synthesized from conventional reagents Li2S and P2S5 (Example 4), and the simulated pattern of Li7P3S11 [2]. [Diagram 5] Results of Le Bail refinement of Examples 3 and 4. Bragg reflections are shown as vertical black lines and the corresponding phases are shown to the right of them. The fits are plotted as solid black lines and the collected data are shown as open black circles. [Figure 6] Deconvolution of signals from structural sites PS4 3-, P2S7 4-, and P2S6 4- in the Raman spectrum of Example 3. The relative ratios of peak areas are also shown in the upper left of the figure. [Figure 7] Deconvolution of signals from structural sites PS4 3-, P2S7 4-, and P2S6 4- in the Raman spectrum of Example 4. The relative ratios of peak areas are also shown in the upper left of the figure. [Figure 8] Comparison of ionic conductivity values ​​versus inverse temperature (1 / T, T in °K) for crystalline Li7P3S11-x / 2Ox / 2 synthesized using Li2CO3 as one of the precursors (Example 3) and crystalline Li7P3S11 synthesized from conventional reagents Li2S and P2S5 (Example 4). EXAMPLES

[0096] Here, the present disclosure will be described with examples, which are intended to illustrate the operation of the present disclosure and are not intended to be understood in a restrictive manner to imply any limitations on the scope of the present disclosure. Other examples are possible that are within the scope of the present disclosure.

[0097] Example 1: Li2S and P2S5 (both from Sigma Aldrich) were used as starting materials. In an Ar-filled glove box, 5 g of total powder with a 2:1 molar ratio was placed in a 45 mL ZrO2 jar containing 15 ZrO2 balls (3 g / ball, 10 mm diameter). The jar was sealed with scotch and parafilm to prevent exposure to air, then removed from the glove box and placed in a Fritsch Planetary Micro Mill Pulverisette 7. The ball mill was milled for 64 hours at a rotation speed of 510 RPM with a 15 minute break every 15 minutes of grinding to prevent excessive heating of the jar. The jar was then transferred to an Ar-filled glove box and the powder was collected. The resulting white powder was then pelletized at 530 MPa using a 10 mm diameter die. The pellets were vacuum sealed in a carbon-coated quartz tube, and the tube was heated to 350 °C at a heating rate of 5 °C / min and kept at the same temperature for 36 hours. After the annealing step, the tube was slowly cooled to room temperature and opened in an Ar-filled glove box.

[0098] The overall reaction on this occasion was: 2Li2S+P2S5=Li4P2S6+S.

[0099] Example 2: 500 mg of Example 1, 76 mg of S8 (Alfa Aesar), and 44 mg of Li2CO3 (Sigma Aldrich) were mixed in a drying room and placed in a 45 mL ZrO2 jar containing 8 ZrO2 balls (3 g / ball, 10 mm diameter). The jar was sealed with scotch and parafilm to prevent exposure to air, then removed from the drying room and placed in a Fritsch Planetary Micro Mill Pulverisette 7. The ball mill was milled for 76 hours at a rotation speed of 510 RPM, with a 15 minute break every 15 minutes of milling to prevent the jar from overheating. The jar was then transferred to an Ar-filled glove box to collect the powder.

[0100] The overall reaction on this occasion was: 3Li4P2S6+4S+Li2CO3=2Li7P3S 10.5 O 0.5 +CO2+S (additional sulfur was added to compensate for possible evaporation of sulfur during the reaction on the left).

[0101] Example 3: Example 2 was pelletized at 530 MPa using a 6 mm diameter die. The pellet was vacuum sealed in a carbon coated quartz tube and the tube was annealed at 260° C. for 1 hour. After the annealing step, the tube was slowly cooled to room temperature and opened in an Ar filled glove box to retrieve the sample.

[0102] Example 4 (Comparative): Li2S and P2S5 (both from Sigma Aldrich) were used as starting materials. In an Ar-filled glove box, 1.5 g of the total powder with a molar ratio of 7:3 was placed in a 45 mL ZrO2 jar containing 12 ZrO2 balls (3 g / ball, 10 mm diameter). The jar was sealed with scotch and parafilm to prevent exposure to air, then removed from the glove box and placed in a Fritzch Planetary Micro Mill Pulverisette 7. The ball mill was milled for 76 hours at a rotation speed of 510 RPM with a 15 minute break every 5 minutes of grinding to prevent excessive heating of the jar. The jar was then transferred to an Ar-filled glove box and the powder was collected. The resulting white powder was pelletized at 530 MPa using a 10 mm diameter die. The pellets were vacuum sealed in a carbon-coated quartz tube and the tube was annealed at 200 °C for 168 hours. After the annealing step, the tube was slowly cooled to room temperature and opened in an Ar-filled glove box.

[0103] The overall reaction on this occasion was: 7Li2S+3P2S5=2Li7P3S 11 It is.

[0104] Characterization Tools: X-ray diffraction of the samples was collected using a Bruker D8 diffractometer with CuKα radiation at room temperature. Prior to the experiment, the samples were sealed in a sample holder with Be in an Ar-filled glove box. Diffraction was collected in the 2θ range of 10°-100° for 13 h. Lattice constants were determined by the Le Bail method used in diffraction profiling using the Full-Prof Suite. Le Bail refinement of the XRD patterns of Examples 3 and 4 was limited to a shorter 2θ range (10°-40°) to increase the accuracy of the lattice constants.

[0105] Raman spectra were collected using a Raman DXR microscope (Thermo Fischer Scientific) with an excitation laser beam of 532 nm wavelength and low laser power of 0.1 mW to prevent excessive heating of the sample. The fitting process was performed using Omnic Software from Thermo Fischer Scientific.

[0106] Prior to impedance spectroscopy measurements, powder samples were cold pressed in an Ar-filled glove box. Powders from Examples 2 and 3 were pressed in a 6 mm diameter die at a pressure of 530 MPa, and powder from Example 4 was pressed in a 10 mm diameter die at a pressure of 530 MPa. The pellets were then sandwiched between pre-dried carbon paper electrodes and then loaded into an airtight sample holder. AC impedance spectra were collected using a Biologic MTZ-35 frequency response analyzer. During the measurements, the AC potential of excitation was set to 50 mV for all samples. The frequency range for the measurements of Example Pellet 2 was 0.05 Hz to 30 MHz, while the range of 1 Hz to 30 MHz was applied for the measurements of pellets from Examples 3 and 4. Spectra for each sample were recorded at stable temperature values, varying between -30°C and 50°C in 10°C increments. Ionic conductivity values ​​were obtained by fitting the data to an equivalent circuit model using ZView software. The slope of the σT vs. 1 / T plot was calculated to determine the activation energy value.

[0107] Experimental Results The Bragg diffraction observed in the XRD pattern of Example 1 correlates with the simulated peak positions of crystalline Li4P2S6 [1], as shown in Figure 1. The Raman spectrum of Example 1 in Figure 2 shows a peak at 383 cm -1 Only the peak centered at P2S6 4-This is due to the vibration of the PS bond of the anion [3, 4]. Therefore, the sample was considered to be phase pure and was used as a precursor for the synthesis of Examples 2 and 3. Without being bound by any theory, the overall reaction observed in Example 1 can be schemed as follows: 2Li2S+P2S5=Li4P2S6+S ↑

[0108] Example 2 was synthesized by mechanochemical synthesis route. After the mechanochemical reaction, P2S7 4- Part and PS4 3- The vibration of the PS bond of the site appears in the Raman spectrum of Example 2. See Figure 2. 4- The signal strength is dramatically reduced, and the structural unit PS4 3- (420cm -1 [5]) and P2S7 4- (405cm -1 [5]) was observed. This is because S and Li2CO3 react with Li4P2S6 to produce P2S6 4- This suggests that the phosphorus ions reacted with the cation site (Example 1) and were thereby oxidized from a formal charge of +4 to +5. 31 A comparison of the P nuclear magnetic resonance (NMR) magic angle spinning (MAS) spectra supports these conclusions; see Figure 3. P2S6 at 108 ppm and 109.4 ppm[6] 4- The decrease in the relative intensity of the signal and the formation of new structural units indicate that PS4 3- For P2S7, 84~86ppm 4- In addition, in Examples 2, 3, and 4, some PO3S is present. 3- (35 ppm[6]) species and P2O7 4- The relatively small amount of oxysulfide and oxide species in Example 4 arises from the limited exposure to moist air during sample preparation, whereas the relatively large amount of oxysulfide and oxide species in Examples 2 and 3 is due to the contribution of O in Li2CO3 to the overall reaction. 2- This comes from the contribution of ions.

[0109] The XRD patterns of Examples 3 and 4, as shown in FIG. 11 The sharper diffraction peaks of Example 4 suggest better overall crystallinity compared to Example 3. Extra diffraction peaks such as those at 2θ=16.6°, 17.4°, 24.3°, 26.8°, 27.4°, 28.9°, and 32.2° are consistent with the Li7P3S of Example 3. 11 This suggests that there are additional crystalline phases in addition to the type phase.

[0110] FIG. 5 shows the Le Bail results of the diffraction patterns of Examples 3 and 4. Example 4 is Li7P3S having the P-1 space group. 11 While Example 3 consists of only Li7P3S type crystal phase, 11 It consists of four crystalline phases: Li3PS4 (Pnma

[13] ), Li4P2S6 (P-31m[3]), and probably Li4P2O7 (P-1

[14] ). 31 The P NMR spectrum shows that P2O7 4- Although the presence of units is suggested, the diffraction peaks of the Li4P2O7 type phase were not clearly observed.

[0111] The results of the Le Bail method (Table 1) show that Li7P3S in Example 3 11 The Li7P3S phase of Example 4 or the Lithium ion exchange reaction 11 This shows that Li7P3S has significantly lower a, b, and c lattice constants than that of Li7P3S. 11 This suggests that the unit cell of the Li7P3S-type phase tends to shrink, resulting in a shorter bond length between PO and a reduced lattice constant compared to PS, signaling the presence of oxide species in the structure

[15] . 11 This confirms that oxygen atoms have been introduced into the crystal structure. 31 Considering the results of P nuclear magnetic resonance (NMR) magic angle spinning (MAS) spectroscopy, Li7P3S in Example 3 11 The type phase is PO3S3- The units exist and in some cases P2O7 4- It can be concluded that units exist.

[0112] [Table 1]

[0113] The Raman spectra of Examples 3 and 4 show a peak at 421 cm -1 , 404cm -1 , and 383 cm -1 In PS4 3- , P2S7 4- , and P2S6 4- This indicates the presence of bond vibrations of the sites. See Figure 2.

[0114] PS4 3- species, P2S7 4- species, P2S6 4- The relative signal ratios between the species were calculated by deconvoluting the Raman spectra of Examples 3 and 4, as shown in Figures 6 and 7. 3- Species and P2S7 4- The relative signal ratio between the species is 11 The expected ratio for Li7P3S was calculated to be 1:1.89 [5, 8]. XRD showed that the crystalline phase (Li7P3S 11 Type, P2S6 4- Since only one P2S6 4- The units were present in an amorphous phase (see Figures 4 and 5). 3- Species and P2S7 4- The relative signal ratio between the species was calculated to be 1:1.28, which is due to the presence of β-Li3PS4, indicating that the material is PS4. 3-

[13] . 4-The relative intensities of the unit peaks are higher in Example 3, which is consistent with the use of Li4P2S6 as synthesized in Example 1 as a precursor, some of which may remain unreacted. These results clearly show that the materials synthesized from the reagents Li2S and P2S5 as in Example 4, and from Li4P2S6 and Li2CO3 as in Example 3, have some similarities in terms of structural properties.

[0115] The ionic conductivities of Examples 3 and 4 as a function of temperature (-30°C to 20°C) are shown in Figure 8. The activation energies were calculated from the σT vs. 1 / T plots using Equation 1:

number

[0116] Example 4 shows a 9×10 catalysis at 20 °C with an activation energy of 0.38 eV, according to literature values ​​[8]. -4 S.cm -1 Example 3 showed a conductivity of 3×10 at 20° C. -4 S.cm -1 and showed a more favorable activation energy of 0.36 eV. The lower conductivity of Example 3 is probably due to crystalline impurities present in the material.

[0117] Results from various characterization tools indicate that the crystalline oxysulfide Li7P3S 11-x / 2 O x / 2 can be synthesized by using Li2CO3, Li4P2S6, and S. This study suggests that Li-PS compounds and Li2CO3 can be used as precursors for the synthesis of Li-PSO oxysulfides.

[0118] Li7P3S 11-x / 2 O x / 2 Li7P3S in (Example 3) 11 The type phases are based on values ​​reported in the literature and on the crystalline Li7P3S synthesized using Li2S and P2S5 as reagents. 11The a, b, and c lattice constants are significantly smaller than those of Example 4. 11-x / 2 O x / 2 Li7P3S in (Example 3) 11 This is evidence that sulfur atoms are replaced by oxygen atoms in the lattice of the Zn-type phase.

[0119] Crystalline β-Li3PS4, Li4P2S6, and possibly Li4P2O7 are formed as by-products. These impurities can potentially be avoided by varying the ball milling in Example 3 (speed, time, cooling dwell time, nature and volume of the ball milling jar, size, nature and amount of ball milling balls, etc.), as well as the annealing time and temperature. Pure Li7P3S 11 (Example 4) and Li7P3S 11-x / 2 O x / 2 The transport properties of Example 3 are of the same order of magnitude. The ionic conductivity of Example 3 may depend on the amount of impurities mentioned above.

[0120] References [1] S. Neuberger, SPCulver, H. Eckert, WG Zeier, J. Schmedt auf der Guenne, Refinement of the crystal structure of Li4P2S6 using NMR crystallography, Dalt. Trans. (2018).doi:10.1039 / C8DT02619J. [2] H. Yamane, M. Shibata, Y. Shimane, T. Junke, Y. Seino, S. Adams, K. Minami, A. Hayashi, M. Tatsumisago, Crystal structure of a superionic conductor, Li7P3S11, Solid State Ionics.178(2007)1163-1167.doi:10.1016 / j.ssi.2007.05.020. [3]C.Dietrich,M.Sadowski,S.Sicolo,D.A.Weber,S.J.Sedlmaier,K.S.Weldert,S.Indris,K.Albe,J.Janek,W.G.Zeier,Local Structural Investigations,Defect Formation,and Ionic Conductivity of the Lithium Ionic Conductor Li4P2S6,Chem.Mater.28(2016)8764-8773.doi:10.1021 / acs.chemmater.6b04175. [4]M.Tachez,J.Malugani,R.Mercier,R.Guy,Ionic conductivity of and phase transition in Li thiophosphate Li3PS4,Solid State Ionics.14(1984)181-185.doi:http: / / dx.doi.org / 10.1016 / 0167-2738(84)90097-3. [5]C.Dietrich,D.A.Weber,S.J.Sedlmaier,S.Indris,S.P.Culver,D.Walter,J.Janek,W.G.Zeier,Lithium ion conductivity in Li2S-P2S5 glasses-building units and local structure evolution during the crystallization of superionic conductors Li3PS4,Li7P3S11 and Li4P2S7,J.Mater.Chem.A.5(2017)18111-18119.doi:10.1039 / C7TA06067J. Inorg.Chem.56(2017)6681-6687.doi:10.1021 / acs.inorgchem.7b00751. [6]S.Kmiec,A.Joyce,S.W.Martin,Glass formation and structural analysis of Na 4 P 2 S 7-x O x ,0≦x≦7 sodium oxy-thiophosphate glasses,J.Non.Cryst.Solids.498(2018)177-189.doi:10.1016 / j.jnoncrysol.2018.06.007. [7]Oe.U.Kudu,T.Famprikis,B.Fleutot,M.-D.Braida,T.Le Mercier,M.S.Islam,C.Masquelier,A review of structural properties and synthesis methods of solid electrolyte materials in the Li2S-P2S5 binary system,J.Power Sources.407(2018)31-43.doi:10.1016 / j.jpowsour.2018.10.037. [8]Y.Wang,D.Lu,M.Bowden,P.Z.El Khoury,K.S.Han,Z.D.Deng,J.Xiao,J.-G.Zhang,J.Liu,Formation mechanism of Li7P3S11 solid electrolytes through liquid phase synthesis,Chem.Mater.30(2018)990-997.doi:10.1021 / acs.chemmater.7b04842. [9]T.Ohtomo,A.Hayashi,M.Tatsumisago,K.Kawamoto,Characteristics of the Li2O-Li2S-P2S 5 glasses synthesized by the two-step mechanical milling,J.Non.Cryst.Solids.364(2013)57-61.doi:10.1016 / j.jnoncrysol.2012.12.044.

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Claims

1. A method for manufacturing a Li-P-S-O product, comprising the following steps: (a) At least Li ４ P ２ S ６ and sulfur, and Li ２ CO ３ Li ２ O, or an oxygen-containing reagent selected from mixtures thereof, and optionally Li ２ S are mixed to obtain a first mixture; (b) heating the first mixture in an inert atmosphere, under vacuum, or under a flow of H ２ S at a temperature included in the range of 150°C to 600°C for a time included in the range of 0.1 hour to 200 hours to produce the Li—P—S—O product; and (c) cooling the Li-P-S-O product and optionally pulverizing it; A method comprising the above steps.

2. wherein the Li—P—S—O product is Li ７ P ３ S １１－ｘ／２ O ｘ／２ , Li ３ PS ４－ｘ／２ O Ｘ／２ , and Li ７ PS ６－５ｘ／２ O ５ｘ／２ (0 < x ≤ 1), the method according to claim 1

3. wherein the oxygen-containing reagent is Li ２ CO ３ The method according to claim 1, comprising

4. The method according to claim 1, wherein the temperature in step (b) is included in the range of 180°C to 300°C.

5. The method according to claim 1, wherein the heating in step (b) is performed for a time included in the range of 0.5 hours to 100 hours.

6. Li ４ P ２ S ６ wherein Li ２ S and P ２ S ５ The method according to claim 1, obtained by the reaction between

7. A Li-P-S-O product obtained by the method according to claim 1.

8. A Li-P-S-O product having a crystal structure of space group P-1 measured by X-ray diffraction and a volume V per formula unit contained in 405 to 415 cubic angstroms at room temperature, of the formula Li ７ P ３ S １１－ｘ／２ O ｘ／２ (0 < x ≤ 1).

9. The Li-P-S-O product according to claim 8, wherein x = 1.

10. Use of the Li-P-S-O product according to any one of claims 7 to 9 as a solid electrolyte, either alone or in combination with any crystalline or amorphous Li material.

11. A solid electrolyte comprising at least one Li-P-S-O product according to any one of claims 7 to 9.

12. - a metal substrate, - a composition (C) in contact with the metal substrate, comprising: (i) a Li-P-S-O product according to any one of claims 7 to 9; (ii) at least one electroactive compound (EAC); (iii) optionally, at least one material that conducts Li ions other than the Li-P-S-O product of the present invention; (iv) optionally, at least one conductive material (ECM); (v) optionally, a lithium salt (LIS); (vi) optionally, at least one polymeric binder material (P); A layer of the composition (C) and An electrode comprising the above components.

13. - a Li-P-S-O product according to any one of claims 7 to 9, - optionally, at least one polymeric binding material (P), - optionally, at least one metal salt, especially a lithium salt, - optionally, at least one plasticizer, A separator comprising the above components.

14. A battery comprising at least one Li-P-S-O product according to any one of claims 7 to 9.

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