Hybrid solid electrolyte (HSE) and processes and uses thereof

Abstract

The present disclosure relates to a hybrid solid electrolyte (HSE) composition having beneficial characteristics, a process for producing said hybrid solid electrolyte (HSE) and uses thereof.

Description

Technical Field

[0001] This invention relates to mixed solid electrolyte compositions. Background Technology

[0002] Lithium-ion batteries (LIBs) are a common technology in electronic devices such as smartphones, laptops, and electric vehicles. Despite substantial progress over the past few decades, conventional lithium-ion batteries (LIBs) still present safety concerns due to their use of highly flammable and toxic liquid electrolytes. Meanwhile, general-purpose technology is nearing its limits, hindering further increases in the range of electric vehicles (EVs). To increase acceptance in electric vehicles and accelerate the transition to more renewable energy sources, a safer technology that offers the potential for higher performance is needed.

[0003] To achieve this, the use of a lithium metal anode has been proposed, based on its low electrochemical potential (-3.04 V) and high theoretical capacity (3860 mAh g⁻¹). -1 This allows for the application of thin anodes. In conventional LIBs, a major obstacle is dendrite formation, which can lead to short circuits and failures, potentially resulting in fires and, in extreme cases, even explosions. All-solid-state batteries (ASSBs) offer the opportunity to overcome this problem by using mechanically stable solid electrolytes (SEs), thereby significantly increasing the available energy density and improving safety.

[0004] Solid electrolytes can be divided into two main categories: organic and inorganic. Organic electrolytes, such as poly(ethylene oxide) (PEO), offer good interfacial contact with electrodes, are easy to process, and are stable for lithium metal anodes. Furthermore, PEO is lightweight and inexpensive, which is beneficial for scalability and application in electric vehicles.

[0005] However, a problem with these materials is their low ionic conductivity at room temperature (RT) (< 0.02 mS / cm). -1 The problem is exacerbated by the partial crystallization of polymers that typically occur at these temperatures and the low lithium transference number (e.g., 0.18 at 80°C). Therefore, materials like PEO can only be used at high temperatures. Inorganic electrolytes can be further divided into thiophosphates and oxides. Oxides such as lithium lanthanum zirconium oxide (LLZO) exhibit high ionic conductivity (0.2 mS / cm at room temperature). -1 This requires a sintering step (> 900℃

[10] ), which results in high energy costs and leads to chemical instability of oxide materials such as LLZO to cathode active materials and the formation of oxide grains.

[0006] Furthermore, materials like LLZO are extremely brittle, making them difficult to manufacture and leading to dendrite formation in the resulting cracks and along grain boundaries. LATP, while exhibiting a lower framework density and higher grain-core conductivity (6 mS / cm),... -1 However, the overall conductivity is limited by the high-resistivity path across grain boundaries. Furthermore, due to the Ti at the anode interface... 4+ The redox reaction of LATP is unstable with lithium metal.

[0007] Thiophosphates (SEs) such as Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 It showed up to 25 mS cm at room temperature. -1 It exhibits high ionic conductivity and a lithium transference number of 1. However, some thiophosphate materials are unstable for lithium anodes. Furthermore, there is a problem in providing adequate contact between thiophosphate particles and with respect to the cathode active material particles, which results in the required high pressure (370 MPa), posing a challenge when considering scaling up.

[0008] Secondly, the possibility of H2S formation after exposure to the atmosphere hinders large-scale production.

[0009] To overcome the drawbacks of organic and inorganic electrolytes, a third type of solid-state membrane (the so-called hybrid solid electrolyte (HSE)) is considered to combine the advantages of each type. Ionic conductivity and lithium transference number are expected to be improved by incorporating filler particles into a polymer matrix (polymer content > 50 wt.-%) or by adding polymers to an inorganic electrolyte (polymer < 50 wt.-%).

[0010] By adding 3 wt.% PEO to Li7P3S 11 (LPS), with ionic conductivity expected to increase from 1.4 mS / cm -1 Increased to 2.1 mS cm -1 However, due to the high LPS content, the challenge of H2S formation remains.

[0011] The manufacture of lithium lanthanum titanate (LLTO) fibers coated with PEO electrolyte is known in the prior art. For a fiber content of 20 wt.-% LLTO, although a 0.5 mS cm⁻¹ was obtained at room temperature... -1 It has high ionic conductivity, but due to the difficulty in manufacturing ceramic fibers, the processing cost is expected to be high.

[0012] On the other hand, it is known that by mixing 2 wt.% Li3PS4 particles into a PEO matrix, an increase in ionic conductivity to as high as 0.035 mS / cm can be observed at 60 °C. -1 .

[0013] According to the published data, a decrease in ionic resistance was observed by incorporating reactive ceramic filler material (LSPS) into the PEO matrix.

[0014] Furthermore, the increasing ionic resistance of agglomerated filler particles underscores the importance of uniform distribution of filler materials. Non-uniform distribution leads to unstable voltage, poor rated capacity, lower capacity, and varying mechanical properties.

[0015] To overcome this problem, adequate dispersion and wetting of the filler particles are necessary.

[0016] Wetting the lithium lanthanum tantalate zirconate (LLZTO) filler particles with an ionic liquid resulted in improved ionic conductivity at room temperature, reaching 0.22 mS / cm. -1 This is a published study.

[0017] Using the published method, higher ionic conductivity was obtained by reducing interfacial resistance, particularly the interfacial resistance between the organic and inorganic components of the resulting mixed electrolyte, through silanization using the chemical bonding of filler particles.

[0018] By using 3 wt.% Li 10 GeP2S 12 (LGPS) was incorporated into the PEO matrix, and at room temperature, a concentration of almost 1 mS / cm was obtained. -1 ionic conductivity.

[0019] To date, there has been little research on the functionalization of filler particles through silanization, and knowledge about the applications of different filler types is lacking.

[0020] What is needed in the art is a hybrid solid electrolyte that can overcome, in whole or in part, one or more of the problems of the prior art. Summary of the Invention

[0021] This invention relates to a mixed solid electrolyte (HSE) composition with beneficial characteristics, a process for producing the mixed solid electrolyte (HSE), and its uses.

[0022] In a first aspect, the present invention relates to a process for producing mixed solid electrolytes (HSEs) based on solvents, comprising the following steps: Provides a suspension of filler particles (FP) in a solvent; A mixture of PEO, PEG, and lithium conductive salts in a solvent is provided; The filler particle suspension from step a) is dispersed in the mixture of PEO, PEG and lithium conductive salt from step b). Optionally, the resulting mixture is degassed; Remove solvent; This results in a mixed solid electrolyte (HSE).

[0023] The mixed electrolytes obtained in this way can be further homogenized and / or processed by other means, such as kneading, layering, coating, extrusion and / or similar methods.

[0024] The uniform distribution of particles in a polymer can be described by the “D-value,” which is derived from microstructural image analysis and measures the free path distance between particles. It quantifies the degree of distribution based on the coefficient of variation. A higher D-value indicates a poorer distribution. Composites with D-values ​​between 0 and 0.25 exhibit very good particle distribution uniformity and are therefore particularly preferred. Materials with D-values ​​between 0 and 0.4, a measure of mixing quality, exhibit mixing quality ranging from very good to satisfactory and are therefore preferred. If the distribution index is greater than 0.4, the mixing quality is no longer satisfactory. The d-value is disclosed in detail in GA Yakaboylu and EM Sabolsky, Determination of a homogeneity factor for composite materials by a microstructural image analysis method. Journal of Microsocpy 266 (2017) 263-272. https: / / doi.org / 10.1111 / jmi.12536, which is incorporated below by reference.

[0025] In a second aspect, the present invention relates to a process for the dry production of mixed solid electrolytes (HSE), comprising the following steps: Provides a suspension of filler particles (FP) in a solvent; PEO, PEG and lithium-ion conductive salt in dry powder form are added simultaneously or sequentially to the mixed aggregate; The particulate suspension obtained in step a) is continuously dispersed in the mixed aggregate; This results in a mixed solid electrolyte (HSE).

[0026] The mixed electrolytes obtained in this way can be further homogenized and / or processed by other means, such as kneading, layering, coating, extrusion and / or similar methods.

[0027] Thirdly, the present invention relates to a mixed solid electrolyte (HSE), comprising: -Thiophosphate or oxide filler particles (FP); - Polymers including polyethylene oxide (PEO) and polyethylene glycol (PEG); - and lithium-ion conductive salts.

[0028] In one implementation, during the kneading process, a PEO / PEG mixture is first prepared, and then the particulate suspension is slowly added to the ongoing process. This is done at a slow rate, allowing sufficient time for the solvent to continue evaporating.

[0029] Fourthly, the present invention relates to an HSE produced by the process disclosed below.

[0030] Fifthly, the present invention relates to a solid electrolyte membrane, comprising the solid electrolyte materials disclosed below.

[0031] In a sixth aspect, the present invention relates to the use of solid electrolyte materials according to the present disclosure in solid-state batteries, which may optionally be all-solid-state lithium-ion batteries.

[0032] Processes for solvent-based production of mixed solid electrolytes (HSE) In one implementation, the process includes the steps outlined above as "the first aspect".

[0033] Methods for producing mixed solid electrolytes (HSEs) based on solvents include several implementations, which are summarized below.

[0034] Filler particles play an important role in HSE because they improve the ionic conductivity of the polymer at room temperature.

[0035] In one embodiment, the filler particles (FP) can be thiophosphate (e.g., LPS) and / or oxide filler particles (e.g., LLZO). In one embodiment, the particles are made of materials having the general formula Li x MeO y The material composition, in one embodiment, is Li. x MeS γ P a (Li = lithium, Me = metal, S = sulfur, P = phosphorus), where 0 ≤ x ≤ 3, Me is selected from metals, P, or B with a valence of n, where n is 3, 4, or 5, and where y = (x + n) / 2. In another embodiment, the particles may be composed of a material having a garnet-like crystalline phase, which has the empirical formula: Li 7+x-y Mx II M 3-x III M 2-y IV My VO 12 M II It is a divalent cation, M III It is a trivalent cation, M IV It is a tetravalent cation, M V It is a pentavalent cation, 0 ≤ x < 3 and 0 ≤ y < 2, or a compound derived therefrom. In another embodiment, the particles may consist of a material having a crystalline phase isomorphic to NaSICon, the material having the empirical formula Li 1+x-y M 5+y M 3+x M 4+2-x-y (PO4)3, where x and y are in the range from 0 to 1, and (1+xy)>1, and M is a cation with a valence of +3, +4, or +5, or a compound derived therefrom. Therefore, in one embodiment, the filler particles may be selected from the group consisting of lithium lanthanum tantalum zirconium oxide (LLZTO), lithium lanthanum zirconium oxide (LLZO), lithium lanthanum titanium oxide (LLTO), lithium superionic phosphorus sulfide (LSPS), lithium garnet phosphorus sulfide (LGPS), lithium phosphorus sulfide (LPS), lithium phosphorus sulfide (LPSCl), lithium aluminum titanium phosphate (LATP), and lithium garnet solids (LGS).

[0036] In one embodiment, the filler particles may be modified before being dispersed in a polymer or polymer electrolyte matrix. Such modification may include milling and / or silanization.

[0037] Grinding reduces particle size and makes the particle size distribution more uniform, both of which positively enhance the overall characteristics of HSE. For example, it has been found that the filler particle size and the structural changes in the filler particles caused by grinding have a significant positive impact on the resulting ionic conductivity.

[0038] Therefore, in one embodiment, the filler particles provided in step a) are ground. In one embodiment, the grinding can be performed by wet grinding.

[0039] Wet grinding is a machining process used in various industries. It involves the wet grinding of materials in a liquid medium (usually water or a solvent). The main purpose of wet grinding is to break down solid particles into smaller, more controllable sizes, or to uniformly disperse substances in a liquid. The mixture is subjected to mechanical forces to reduce the size of the solid particles and achieve the desired particle size distribution. This is typically done in specialized equipment such as ball mills, bead mills, or grinding mills. The grinding action can be achieved by various methods, including impact, shearing, and friction. In one embodiment, alcohols (especially ethanol or isopropanol), ketones (especially acetone or methyl ethyl ketone), acetonitrile, N-methyl-1-pyrrolidone (NMP), N,N-dimethylacetamide, or dimethyl carbonate are used as the wet medium in the wet grinding process.

[0040] In one embodiment, the solid content may be between 5 and 80 wt.%, between 8 and 70 wt.%, between 10 and 65 wt.%, and / or about 50 wt.%. Optionally, milling is performed until the particle size is 5 μm or less in diameter, 3 μm or less in diameter, 1 μm or less in diameter, and / or 0.8 μm or less in diameter. In one embodiment, wet milling may be carried out in a solvent selected from the group consisting of alcohols (especially ethanol or isopropanol), ketones (especially acetone or methyl ethyl ketone), acetonitrile, N-methyl-1-pyrrolidone (NMP), N,N-dimethylacetamide, or dimethyl carbonate, and mixtures thereof.

[0041] In one embodiment, after the grinding process, the mixture containing filler particles undergoes a drying step until the filler particles are dry. In one embodiment, the term "dry" means that the residual solvent content is less than 1 wt.-%, less than 0.75 wt.-%, less than 0.5 wt.-%, less than 0.25 wt.-%, less than 0.1 wt.-%, and less than 0.05 wt.-%. In one embodiment, the mixture is solvent-free. The drying process can be carried out in a drying chamber. In one embodiment, the final drying will optionally be carried out in a batch or continuously operating heated drying oven at medium (up to 200°C) or even high (>200°C). Pre-drying can be carried out in a freeze dryer or on a rotary evaporator, while the final drying is carried out in a batch or continuously operating heated drying oven at medium (up to 200°C) or even high (>200°C). Drying chambers can also be used during battery construction because some battery materials are sensitive to moisture, and water that enters through contact with humid air can affect the function of the final manufactured battery.

[0042] The disclosed feature is that the silanization of the filler particles significantly improves the overall characteristics of HSE.

[0043] The term "silanization" is defined here as a chemical process used to modify the surface properties of a material. This process involves applying a silane coupling agent (commonly referred to as a silane or silane primer) to the surface of a substrate. Silanes are compounds containing silicon atoms (Si) bonded to an organic group (R), typically denoted as Si-R3.

[0044] It has been found that chemical bonding between polymers and active filler particles via silanization leads to an increase in the ionic conductivity of the HSE (Hydrogen Sediment). Furthermore, successful silanization can significantly improve the stability of the suspension. Throughout this application, silanized particles are also referred to as "functionalized" particles.

[0045] Therefore, in one embodiment, the filler particles provided in step a) (according to the first aspect of this disclosure) can react on their surface with a silane according to one of the following formulas: (X2) n Si(R1-X1) 4-n Or (X2) n Si(R1-X1) m (R2) 4-(m+n) , The silane has at least one silicon atom, which carries one to three leaving groups X1 (e.g., alkoxy, acyloxy, Cl-, or H- atoms) as reactive groups, which can be chemically bonded to the particle surface during functionalization. On the other hand, at least one or more of three reactive groups (R1-X1) – themselves composed of bridging groups R1 and leaving groups X1 – and zero, one, or at most two non-reactive groups (R2) are bonded to the silicon atom, which remain there after successful silane bonding. Through additional reaction with leaving groups X1, PEG molecules attach to the silane side groups. In summary, this significantly alters the surface chemistry of the particle surface compared to unfunctionalized particles, thereby changing the interaction with the HSE polymer components (i.e., w / o silanization). In one embodiment, X2 = methoxy (-OCH3), X1 = Cl, R = methylphenethyl, n = 3, i.e., (chloromethyl)(phenethyl)trimethoxysilane.

[0046] In one embodiment, the silane may be selected from the group consisting of (chloromethyl)(phenylethyl)trimethoxysilane (CTMS) and / or chloropropyltrimethoxysilane, and combinations thereof. In one embodiment, chloropropyltrimethoxysilane is excluded from the selected silanes.

[0047] In one embodiment, silanization can be performed at a temperature between 50°C and 70°C, optionally around 60°C. In another embodiment, silanization is performed under stirring, for example, using a magnetic stirrer.

[0048] In another embodiment, silanization is performed after the filler particles are milled. In yet another embodiment, silanization is performed before the filler particles are milled. However, silanization can also be performed before, during, and / or after particle milling. In one embodiment, silanization occurs after particle milling.

[0049] In one embodiment, the solvent used in step b (according to the first aspect of this disclosure) may be selected from the group consisting of alcohols (e.g., ethanol or isopropanol), ketones (especially acetone or methyl ethyl ketone), acetonitrile, N-methyl-1-pyrrolidone (NMP), N,N-dimethylacetamide, or dimethyl carbonate, and mixtures thereof. In another embodiment, the dissolution time (step b) (according to the first aspect of this disclosure) may be between 0 and 48 hours, between 0.25 and 45 hours, between 0.5 and 40 hours, between 1 and 36 hours, between 2 and 28 hours, and in one embodiment about 12 hours. Dissolution may take 1 hour or longer, 2 hours or longer, 5 hours or longer, 12 hours or longer, 24 hours or longer, or 48 hours or longer.

[0050] In one embodiment, step c is facilitated by using a device selected from a shaker, a magnetic stirrer (optionally with an agitator), and a dissolver (according to a first aspect of this disclosure).

[0051] In one embodiment, the PEO:PEG ratio in step c) (according to a first aspect of this disclosure) is between 3:1 and 5:1, and optionally, the PEO:PEG ratio is about 4:1. A PEO:PEG ratio of about 80:20 wt.-% (or 4:1 wt.-%), or between 65:35 wt.-% and 90:10 wt.-% and / or 3:1 wt.-% to 5:1 wt.-% has been found to be most suitable for achieving excellent HSE results.

[0052] "PEO" and "PEG" are both acronyms for polyethylene oxide (PEO) and polyethylene glycol (PEG). Although they have similar structures and are often used interchangeably, there are subtle differences between them.

[0053] PEO is a polymer composed of repeating ethylene oxide units, which are composed of oxygen and carbon atoms (CH2-CH2-O). n It consists of simple repeating units. PEO is highly hydrophilic, meaning it has a strong affinity for water. It can form hydrogen bonds with water molecules, making it soluble in water.

[0054] Like PEO, PEG is also a polymer composed of repeating ethylene oxide units. The shorter the chain, the higher the density of OH groups. This alters the chemical properties of the polymer chain, thus making it correspondingly more reactive with the X1 functional groups / leaving groups in the silane side groups.

[0055] The term "polyethylene glycol (PEG)" is used here for polyethylene glycol with an average molecular weight of 200 to 35,000 g / mol. Products with higher molecular weights (starting from about 35,000 g / mol) are referred to below as "polyethylene oxide (PEO)" because the effect of the terminal hydroxyl groups can be neglected in PEO.

[0056] In one embodiment, the "conductive salt" or "lithium-ion conductive salt" in step b) (according to the first aspect of this disclosure) may be selected from LiAsF6, LiClO4, LiSbF6, LiPtCl6, LiAlCl4, LiGaCl4, LiSCN, LiAlO4, LiCF3CF2SO3, Li(CF3)SO3 (LiTf), LiC(SO2CF3)3, LiPF6, LiPF3(CF3)3 (LiFAP), LiPF4(C2O4) (LiTFOB), LiBF4, LiB(C2O4)2 (LiBOB), LiBF2(C2O4) (LiDFOB), LiB(C2O4)(C3O4) (LiMOB), Li(C2F5BF3) (LiFAB), Li2B 12 F 12 The group consisting of (LiDFB), LiN(FSO2)2 (LiFSI), LiN(SO2CF3)2 (LiTFSI), LiN(SO2C2F5)2 (LiBETI)LiClO4, lithium bis(oxalate)borate, lithium difluoro(oxalate)borate, LiSO3CF3, lithium 2-pentafluoroethoxy-1,1,2,2-tetrafluoroethanesulfonate, and lithium 2-pentafluoroethoxy-1,1,2,2-tetrafluoroethanesulfonate (LiSO3C2F4OC2F5), and combinations thereof.

[0057] In one embodiment, the dispersion in step c) (according to the first aspect of this disclosure) can be run at a low speed in a dispersion device for a period of time between 1 and 10 minutes at a speed between 1,000 and 3,000 rpm, optionally about 2,000 rpm, and then optionally at a high speed for a period of time between 15 and 60 minutes at a speed between 4,000 and 6,000 rpm, optionally about 5,000 rpm.

[0058] In one embodiment, the time for dispensing step c (according to the first aspect of the present disclosure) can be between 0 and 48 hours, optionally about 12 hours or less, 6 hours or less, 1 hour or less, or 5 minutes or less. In one embodiment, the time for dispersion (step c) (according to the second aspect of the present disclosure) can be slow enough to allow solvent evaporation, for example within at least 1 minute, at least 5 minutes, at least 30 minutes, at least 1 hour, at least 2 hours, at least 3 hours, or at least 6 hours.

[0059] In one embodiment, the dispersing apparatus in dispersing step c) (according to the first aspect of this disclosure) is selected from the group consisting of a rocker, a magnetic stirrer (optionally with an agitator), and a dissolver.

[0060] In a further embodiment, the optional degassing step may be accomplished by storing the suspension produced in step c) (according to the first aspect of this disclosure) for 30 minutes or longer, 1 hour or longer, 3 hours or longer, 6 hours or longer, 12 hours or longer, 24 hours or longer, 48 hours or longer, 96 hours or longer, 7 days or longer, or optionally 2 weeks or longer. In yet another embodiment, the degassing step may be carried out in a vacuum chamber at a pressure of about 1000 Pa or lower, about 500 Pa or lower, about 100 Pa or lower, about 50 Pa or lower, or about 10 Pa or lower.

[0061] In a further embodiment, the process is followed by an additional step in which the HSE is coated onto the surface to produce an HSE film. In another embodiment, the HSE is calendered; in yet another embodiment, the HSE is passed through a three-roll mill, kneader, or extruder to improve its uniformity.

[0062] Processes for dry production of HSE In one implementation, the process includes steps outlined above as "the second aspect".

[0063] The process for dry production of mixed solid electrolytes (HSE) includes several implementations, which are summarized below.

[0064] The process for dry production of HSE is largely similar to the solvent-based process according to the "First Aspect". However, the biggest difference between the two process variations is that the polymer or polymer mixture containing a conductive salt is premixed in a kneader without any solvent added, in powder form, and then the particles are added as a granular suspension containing a silanizing agent in addition to the particles. In some embodiments, another dispersing tool such as an extruder, a three-roll mill, or the like can also be used instead of a kneader. The granular suspension added during formulation evaporates, so that the actual mixing step c) (according to the "Second Aspect" of this disclosure) is carried out in a dry state. Apart from these differences, the features of the "First Aspect" and the "Second Aspect" are interchangeable. In one embodiment, the particles may also be introduced into the process in a dry form, i.e., as a powder, i.e., without any solvent. In such an embodiment, the solvent is used only to dissolve the silanizing agent, and the particles are added as a "dry powder" later in the process after the solvent has evaporated.

[0065] Similarly, in dry production processes, filler particles play an important role in HSE because they improve the ionic conductivity of the polymer at room temperature.

[0066] In one embodiment, the filler particles (FP) can be thiophosphate (e.g., LPS) and / or oxide filler particles (e.g., LATP). In one embodiment, the particles are made of materials having the general formula Li x MeO y The material composition, wherein 0 ≤ x ≤ 3, Me is selected from metals with a valence of n, P, or B, where n is 3, 4, or 5, and y = (x + n) / 2. In another embodiment, the particles may be composed of a material having a garnet-like crystal phase, the empirical formula of which is: Li 7+x-y Mx II M 3-x III M 2-y IV My V O 12 M II It is a divalent cation, M III It is a trivalent cation, M IV It is a tetravalent cation, M V It is a pentavalent cation, 0 ≤ x < 3 and 0 ≤ y < 2, or a compound derived therefrom. In another embodiment, the particles may consist of a material having a crystalline phase isomorphic to NaSICon, the material having the empirical formula Li 1+x-y M 5+y M 3+x M 4+2-x-y(PO4)3, where x and y are in the range from 0 to 1, and (1+xy)>1, and M is a cation with a valence of +3, +4, or +5, or a compound derived therefrom. Therefore, in one embodiment, the filler particles may be selected from the group consisting of lithium lanthanum tantalum zirconium oxide (LLZTO), lithium lanthanum zirconium oxide (LLZO), lithium lanthanum titanium oxide (LLTO), lithium superionic phosphorus sulfide (LSPS), lithium garnet phosphorus sulfide (LGPS), lithium phosphorus sulfide (LPS), lithium phosphorus sulfide (LPSCl), lithium aluminum titanium phosphate (LATP), and lithium garnet solids (LGS).

[0067] In one embodiment, the filler particles may be modified before being dispersed in a polymer or polymer electrolyte matrix. Such modification may include milling and / or silanization.

[0068] Grinding reduces particle size and makes the particle size distribution more uniform, both of which positively enhance the overall characteristics of HSE. For example, it has been found that the filler particle size and the structural changes in the filler particles caused by grinding have a significant positive impact on the resulting ionic conductivity.

[0069] Therefore, in one embodiment, the filler particles provided in step a) (according to the second aspect of this disclosure) are ground. In one embodiment, the grinding can be performed by wet grinding.

[0070] In one embodiment, milling can be carried out for a time between 2 and 60 minutes, 5 and 45 minutes, and 10 and 30 minutes. In another embodiment, milling is carried out for less than 1 hour, less than 45 minutes, and less than 30 minutes. In yet another embodiment, particularly in large batches used on an industrial scale, milling can be carried out for a time between 1 hour and 3 days, between 2 hours and 48 hours, or between 3 hours and 24 hours. In one embodiment, milling is carried out for less than 12 hours, less than 6 hours, or less than 3 hours. Milling can be carried out at speeds between 100 and 5000 rpm, between 200 and 4500 rpm, or between 300 and 4000 rpm. In one embodiment, the solids content can be between 5 and 20 wt.% , between 8 and 18 wt.% , between 10 and 15 wt.% , and / or about 10 wt.% . Optionally, milling is carried out until the particle size is 5 μm or less in diameter, 3 μm or less in diameter, 1 μm or less in diameter, and / or 0.8 μm or less in diameter. In some embodiments, milling is performed until the particle size is 500 nm or smaller, 300 nm or smaller, or 100 nm or smaller. In one embodiment, wet milling can be carried out in a solvent selected from the group consisting of alcohols (especially ethanol or isopropanol), ketones (especially acetone or methyl ethyl ketone), acetonitrile, N-methyl-1-pyrrolidone (NMP), N,N-dimethylacetamide, or dimethyl carbonate, and mixtures thereof.

[0071] Following the grinding process, in one embodiment, the mixture containing filler particles undergoes a drying step until the filler particles are dry. In one embodiment, the term "dry" means that the residual solvent content is less than 1 wt.-%, less than 0.75 wt.-%, less than 0.5 wt.-%, less than 0.25 wt.-%, less than 0.1 wt.-%, and less than 0.05 wt.-%. In one embodiment, the mixture is solvent-free. The drying process can be carried out in a drying chamber. In one embodiment, evaporation should not be carried out in open atmosphere but under controlled conditions; in one embodiment, evaporation is carried out in a closed device that allows for controlled recondensation and solvent collection (for reprocessing for reuse or at least for controlled disposal).

[0072] In one embodiment, final drying may optionally be carried out in a batch or continuously operating heated drying oven at medium (up to 200°C) or even high (>200°C) temperatures. Pre-drying can be performed in a freeze dryer or rotary evaporator, while final drying is carried out in a batch or continuously operating heated drying oven at medium (up to 200°C) or even high (>200°C) temperatures. Drying chambers may also be used during battery construction because some battery materials are sensitive to moisture, and water introduced through contact with humid air can affect the function of the final manufactured battery.

[0073] The disclosed invention relates to the significant improvement in the overall characteristics of HSE (Hydrogen Sediment) through the silanization of filler particles. It has been found that the chemical bonding between the polymer and the active filler particles via silanization increases the ionic conductivity of the HSE. Furthermore, the stability of the suspension can be significantly improved through successful silanization. In this application, silanized particles are also referred to as "functionalized" particles.

[0074] Therefore, in one embodiment, the filler particles provided in step a) (according to the second aspect of this disclosure) can react on their surface with a silane according to one of the following formulas: (X2) n Si(R1-X1) 4-n Or (X2) n Si(R1-X1) m (R2) 4-(m+n) , The silane has at least one silicon atom, which carries one to three leaving groups X2 (e.g., alkoxy, acyloxy, Cl-, or H- atoms) as reactive groups, enabling chemical bonding to the particle surface during functionalization. On the other hand, at least one or up to three reactive groups (R1-X1) – themselves composed of bridging groups R1 and leaving groups X1 – and zero, one, or at most two non-reactive groups (R2) are bonded to the silicon atom, remaining there after successful silane bonding. Through additional reaction with the leaving group X1, PEG molecules attach to the silane side groups. In summary, this significantly alters the surface chemistry of the particle surface compared to unfunctionalized particles, thereby changing the interaction with the HSE polymer components (i.e., w / o silanization). In one embodiment, in the above formula, X2 = methoxy (-OCH3), X1 = Cl, R = methylphenethyl, n = 3, i.e., (chloromethyl)(phenethyl)trimethoxysilane.

[0075] In one embodiment, the silane may be selected from the group consisting of (chloromethyl)(phenylethyl)trimethoxysilane (CTMS) and / or chloropropyltrimethoxysilane, and combinations thereof. In one embodiment, chloropropyltrimethoxysilane is excluded from the selected silanes.

[0076] In one embodiment, silanization can be carried out at a temperature between 50°C and 70°C, optionally around 60°C. In another embodiment, silanization is carried out with stirring using a magnetic stirrer.

[0077] In another embodiment, silanization is performed after the filler particles are milled. In yet another embodiment, silanization is performed before the filler particles are milled. However, silanization can be performed before, during, and / or after particle milling. In one embodiment, silanization is performed after milling.

[0078] In one embodiment, the solvent used in step b) may be selected from the group consisting of alcohols (especially ethanol or isopropanol), ketones (especially acetone or methyl ethyl ketone), acetonitrile, N-methyl-1-pyrrolidone (NMP), N,N-dimethylacetamide, or dimethyl carbonate, and mixtures thereof. In another embodiment, the dissolution time (step b) may be between 0 and 48 hours, between 3 and 45 hours, between 6 and 40 hours, between 8 and 36 hours, between 12 and 28 hours, and in one embodiment approximately 24 hours. Dissolution may take 12 hours or longer, 24 hours or longer, or 48 hours or longer.

[0079] In one embodiment, dissolution is facilitated by using a device selected from a shaker, a magnetic stirrer (optionally equipped with an agitator), and a dissolver.

[0080] In one embodiment, the PEO:PEG ratio in step c) (according to a second aspect of this disclosure) is between 3:1 and 5:1, and optionally, about 4:1. A PEO:PEG ratio of about 80:20 wt.-% (or 4:1 wt.-%), or between 65:35 wt.-% and 90:10 wt.-% and / or 3:1 wt.-% to 5:1 wt.-% has been found to be most suitable for achieving excellent HSE results.

[0081] In one embodiment, the lithium-ion conductive salt in step c) can be selected from LiAsF6, LiClO4, LiSbF6, LiPtCl6, LiAlCl4, LiGaCl4, LiSCN, LiAlO4, LiCF3CF2SO3, Li(CF3)SO3 (LiTf), LiC(SO2CF3)3, LiPF6, LiPF3(CF3)3 (LiFAP), LiPF4(C2O4) (LiTFOB), LiBF4, LiB(C2O4)2 (LiBOB), LiBF2(C2O4) (LiDFOB), LiB(C2O4)(C3O4) (LiMOB), Li(C2F5BF3) (LiFAB), Li2B 12 F 12 The group consisting of (LiDFB), LiN(FSO2)2 (LiFSI), LiN(SO2CF3)2 (LiTFSI), LiN(SO2C2F5)2 (LiBETI)LiClO4, lithium bis(oxalate)borate, lithium difluoro(oxalate)borate, LiSO3CF3, lithium 2-pentafluoroethoxy-1,1,2,2-tetrafluoroethanesulfonate, lithium 2-pentafluoroethoxy-1,1,2,2-tetrafluoroethanesulfonate (LiSO3C2F4OC2F5), and combinations thereof.

[0082] In one implementation, the mixing time is between 1 minute and 2 hours, or between 5 minutes and 1 hour. In some implementations, the mixing time is 45 minutes or less, or 30 minutes or less.

[0083] In one implementation, the kneading torque (M / Nm) is between 1 and 20, between 4 and 15, between 5 and 14, between 6 and 13, and between 8 and 12.

[0084] In one implementation, the kneading (step c) time is between 0 and 48 hours, optionally about 24 hours or less, 12 hours or less.

[0085] In another embodiment, a drying step may be performed to remove any remaining solvent residue. This can be carried out in a vacuum chamber at pressures of about 1000 Pa or lower, about 500 Pa or lower, about 100 Pa or lower, about 50 Pa or lower, or about 10 Pa or lower. However, other drying processes, such as standard thermal activation drying at atmospheric pressure, may also be considered in this case.

[0086] In a further embodiment, an additional step is performed after the process in which HSE is coated onto the surface to produce an HSE film. In another embodiment, the HSE is calendered. In one embodiment, the HSE is coated onto a carrier film, for example, made of Mylar or Teflon (PTFE). In such embodiments, the HSE film can then be removed relatively easily. In this case, it is preferable to pour the slurry produced after wet silanization onto the carrier film before the drying step.

[0087] Mixed solid electrolytes (HSE) This disclosure also relates to an improved HSE, which is described below and produced by any method according to the first and / or second aspects of this disclosure.

[0088] In one embodiment, the filler particles (FP) in the HSE can be thiophosphate (e.g., LPS) and / or oxide filler particles (e.g., LLZO).

[0089] In one embodiment, the particles are composed of particles having the general formula Li x MeO y The material composition is such that 0 ≤ x ≤ 3, Me is selected from metals with a valence of n, P, or B, where n is 3, 4, or 5, and y = (x + n) / 2. In another embodiment, the particles may be composed of a material having a garnet-like crystal phase, the empirical formula of which is: Li 7+x-y Mx II M 3-x III M 2-y IV My V O 12 M II It is a divalent cation, M III It is a trivalent cation, M IV It is a tetravalent cation, M V It is a pentavalent cation, 0 ≤ x < 3 and 0 ≤ y < 2, or a compound derived therefrom. In another embodiment, the particles may consist of a material having a crystalline phase isomorphic to NaSICon, the material having the empirical formula Li 1+x-y M 5+y M 3+x M 4+2-x-y(PO4)3, where x and y are in the range from 0 to 1, and (1+xy)>1, and M is a cation with a valence of +3, +4, or +5, or a compound derived therefrom. Therefore, in one embodiment, the filler particles may be selected from the group consisting of lithium lanthanum tantalum zirconium oxide (LLZTO), lithium lanthanum zirconium oxide (LLZO), lithium lanthanum titanium oxide (LLTO), lithium superionic phosphorus sulfide (LSPS), lithium garnet phosphorus sulfide (LGPS), lithium phosphorus sulfide (LPS), lithium phosphorus sulfide (LPSCl), lithium aluminum titanium phosphate (LATP), lithium garnet solids (LGS), and / or mixtures thereof.

[0090] In one embodiment, the average diameter x of the filler particles 50 For 5 μm or smaller, 3 μm or smaller, or 1 μm or smaller.

[0091] In one embodiment, the final content of filler particles (FP) in the mixed solid electrolyte (HSE) is between >0 vol.-% and 15 vol.-%, between 3 vol.-% and 12 vol.-%, between 6 vol.-% and 11 vol.-%, and optionally about 10 vol.-%.

[0092] In one embodiment, the filler particles in the HSE are silanized and / or milled, wherein the silane may be selected from the group consisting of (chloromethyl)(phenylethyl)trimethoxysilane (CTMS) and / or chloropropyltrimethoxysilane and combinations thereof. In one embodiment, chloropropyltrimethoxysilane is excluded from the selected silanes. In one embodiment, milling may optionally be performed by wet milling in isopropanol.

[0093] In one embodiment, the PEO:PEG ratio in step c) of the PEO:PEG mixture is between 3:1 and 5:1, and optionally, the PEO:PEG ratio is about 4:1. A PEO:PEG ratio of about 80:20 wt.-% (or 4:1 wt.-%), or between 65:35 wt.-% and 90:10 wt.-% and / or 3:1 wt.-% to 5:1 wt.-% has been found to be most suitable for achieving excellent HSE results.

[0094] In one embodiment, a solid polymer electrolyte for manufacturing polyethylene oxide (Mw = 900,000 g / mol) (Dow) and optionally polyethylene glycol (Mw = 2,000 g / mol) and lithium salt bis(trifluoromethane)sulfonylimide (LiTFSI) (Clariant) are used in molar ratios of Li / EO 20:1, Li / EO 14:1, Li / EO 7:1, Li / EO 1:1, Li / EO 1:5, Li / EO 1:7, Li / EO 1:14, and Li / EO 1:20.

[0095] In one embodiment, the lithium-ion conductive salt in step b) (according to the first or second aspect of this disclosure) is selected from LiAsF6, LiClO4, LiSbF6, LiPtCl6, LiAlCl4, LiGaCl4, LiSCN, LiAlO4, LiCF3CF2SO3, Li(CF3)SO3 (LiTf), LiC(SO2CF3)3, LiPF6, LiPF3(CF3)3 (LiFAP), LiPF4(C2O4) (LiTFOB), LiBF4, LiB(C2O4)2 (LiBOB), LiBF2(C2O4) (LiDFOB), LiB(C2O4)(C3O4) (LiMOB), Li(C2F5BF3) (LiFAB), Li2B 12 F 12 The group consisting of (LiDFB), LiN(FSO2)2 (LiFSI), LiN(SO2CF3)2 (LiTFSI), LiN(SO2C2F5)2 (LiBETI)LiClO4, lithium bis(oxalate)borate, lithium difluoro(oxalate)borate, LiSO3CF3, lithium 2-pentafluoroethoxy-1,1,2,2-tetrafluoroethanesulfonate, lithium 2-pentafluoroethoxy-1,1,2,2-tetrafluoroethanesulfonate (LiSO3C2F4OC2F5), and combinations thereof.

[0096] In one embodiment, no H2S formation was detected within 48 hours, 96 hours, 1 week, 2 weeks, 3 weeks, and 4 weeks after HSE production. In one embodiment, the interface resistance of the HSE (at 20°C) is 200 Ω or less, 100 Ω or less, 80 Ω or less, 75 Ω or less, 65 Ω or less, 60 Ω or less, and 50 Ω or less.

[0097] "Interface resistance" is the resistance between filler particles and polymer solid electrolyte (PSE).

[0098] For lithium metal symmetric batteries, when at 0.1 mA / cm 2During stripping-electroplating experiments at 80°C and at the specified current density, a constant voltage was obtained for HSEs with functionalized LPS particles, while a sharp voltage increase of up to 0.5 V was observed over time for unfunctionalized particles. After 190 h, the unfunctionalized cells exhibited a large voltage drop due to short circuits. If the LPS is in direct contact with the lithium metal electrode, the voltage increase is attributed to stability issues. After a slight increase in overpotential initially (40 mV), a low polarization voltage (3 mV) was observed for HSEs with functionalized LPS. Functionalization suppresses direct contact between the LPS particles and the lithium metal interface, thereby improving cycle stability. In one embodiment, the polarization voltage of the HSE (at 80°C) is 50 mV or less, 40 mV or less, 5 mV or less, or 3 mV or less.

[0099] In one embodiment, the porosity (ε / %) of the HSE is 10.00 or less, 9.53 or less, 8.24 or less, 2.34 or less, 0.62 or less, or 0.35 or less.

[0100] In one embodiment, the ionic conductivity of HSE at room temperature (RT) is 1.4 × 10⁻⁶. -5 S cm -1 and 6.2*10 -5 Scm -1 between.

[0101] In one embodiment, the lithium-ion transference number in the HSE is 0.12 or greater, 0.52 or greater, 0.55 or greater, 0.57 or greater, or 0.6 or greater.

[0102] In one embodiment, the crystallite size of the particulate filler in the HSE is 20 nm or larger, optionally 35 nm or larger, or 50 nm or larger.

[0103] HSEs produced by any of the processes disclosed below are also disclosed.

[0104] In one embodiment, HSE is further characterized by an effective volume fraction df value less than 2, less than 1.5, or less than 1. "Effective volume fraction" reflects the agglomeration effect of the filler in the composite material. This is a statistical measure that helps in understanding the bimodal distribution of particles or clusters in the matrix. This parameter helps in a more in-depth quantitative understanding of particle dispersion and its impact on the mechanical properties of the composite material.

[0105] The dispersion factor df is used as a measure of microstructure uniformity. It is defined as the ratio between the average area µ of visible particles / clusters in the image and the standard deviation σ, where df = σ / µ.

[0106] Composite materials with a df value less than 1 exhibit very good particle distribution uniformity and are therefore particularly preferred. As a measure of mix quality, materials with a df value less than 2 exhibit very good to satisfactory mix quality and are therefore preferred. If the distribution index value is greater than 2, the mix quality is no longer satisfactory.

[0107] "Effective volume fraction" and df in GE Rani, R. Murugeswari, S. Siengchi N, N. Rajini, MA Kumar's Quantitative assessment of particle dispersion in polymeric composites and its effect on mechanical properties Journal of Materials Research and Technology A more detailed description can be found in 19 (2022) 1836-1845, https: / / doi.org / 10.1016 / j.jmrt.2022.05.147, which is incorporated below by reference.

[0108] Uses of HSE In another embodiment, the use of a solid electrolyte material in a solid-state battery is disclosed, which may optionally be an all-solid-state lithium-ion battery.

[0109] All-solid-state lithium-ion batteries (ASSBs) are rechargeable batteries in which all components, including the electrolyte, are made of solid materials, rather than the traditional liquid or gel electrolytes found in conventional lithium-ion batteries (LIBs). ASSBs have gained significant attention in recent years because of their potential to address the safety, energy density, and performance limitations associated with liquid electrolyte-based LIBs.

[0110] The components of an all-solid-state lithium-ion battery typically include: Cathode: The cathode is typically made of lithium-containing compounds, such as lithium cobalt oxide (LiCoO2), lithium iron phosphate (LiFePO4), or other lithium transition metal oxides. It serves as the positive electrode and stores lithium ions during charging and discharging.

[0111] • Anode: The anode is typically made of lithium-containing materials, usually lithium metal (Li), although other materials such as lithium titanium oxide (Li₄Ti₅O₃) can also be used. 12 Lithium ions are released at the anode during discharge and stored at the anode during charging.

[0112] Solid electrolyte: The key component that distinguishes ASSB from conventional LIB is the solid electrolyte. In this disclosure, it is the disclosed HSE.

[0113] Separator: Similar to conventional LIBs, ASSBs have a separator that physically isolates the cathode and anode to prevent short circuits while allowing lithium ions to flow.

[0114] In the case of ASSB, the separator is composed of a solid electrolyte. In the case of LIB, the separator is composed of an inert porous (composite) material that can be permeated by a liquid electrolyte.

[0115] Key advantages of all-solid-state lithium-ion batteries: Enhanced safety: One of the main benefits of ASSB compared to conventional LIBs with liquid electrolytes is improved safety. Solid electrolytes are less prone to leakage, thermal runaway, and dendrite formation (protruding lithium metal structures can cause short circuits).

[0116] Higher energy density: ASSBs have the potential to offer higher energy density, meaning they can store more energy in the same amount of space. This can enable longer battery life or smaller, lighter battery packs.

[0117] Wide operating temperature range: Compared to liquid electrolytes, solid electrolytes typically have a wider operating temperature range, making ASSB suitable for extreme temperature conditions.

[0118] Longer cycle life: Compared to conventional LIBs, ASSBs can have a longer cycle life and lower capacity degradation over time.

[0119] The HSE disclosed herein can be used at a variety of temperatures, which is important in certain applications. Thus, in one embodiment, the disclosed HSE can be used at temperatures between -60°C and 100°C, optionally between -40°C and 80°C.

[0120] Another embodiment relates to the use of solid electrolyte materials in electric vehicles, portable electronic devices, energy storage, space exploration, medical technologies (e.g., pacemakers), industrial applications (e.g., backup power supplies and high-performance equipment), aerospace (e.g., energy storage solutions for aircraft, satellites and spacecraft), distributed energy systems and / or emergency and rescue technologies. Attached Figure Description

[0121] This application includes at least one color illustration. The above and other features and advantages of the invention, as well as the ways in which they are obtained, will become more apparent and the invention will be better understood from the following description of embodiments of the invention in conjunction with the accompanying drawings, wherein: Figure 1(a) and (b) are explained as follows: (a) Ionic conductivity of HSE was measured with 1 vol.-% LPS, depending on the dissolution time before and after dispersion in a dissolver. (b) Ionic conductivity and residual porosity were measured using a dispersion apparatus consisting of PEO-PEG-LiTFSI-1 vol.-% LPS. Figure 2 ((a), (b), (c), (d)) Explanation: Specific ionic conductivity is depicted as a function of LPS content at 20 °C (a). Raman spectroscopy analysis of the deposited suspension material is shown (b); (c) shows photographs of suspensions with and without silane (left) and porosity of HSEs with and without silane functionalization; (d) shows the specific ionic conductivity as a function of temperature for a polymer solid electrolyte (PSE) as a reference and HSEs with different LPS contents and silane functionalization. Figure 3 ((a), (b)) Explanation: Shows the possible transmission paths of HSE through functionalized LPS particles with (a) and without (b); Figure 4 ((a), (b)) Explanation: Shows the reaction mechanism of LPS and CTMS and the addition of functionalized LPS particles to PEO (a), and TGA analysis of the original and functionalized LPS particles (b). Figure 5 ((a), (b), (c), (d)) Explanation: Shows SEM images of HSE with 1 vol.% LPS at 1.10k (a) and 10.0k (b) resolution, and HSE with 1 vol.% LPS and silane-functionalized LPS at 1.20k (c) and 10.0k (d) resolution; Figure 6 ((a), (b), (c), (d)) Explanation: For unfunctionalized HSE, H2S formation dependent on exposure time to ambient air is shown in (a); lithium interface resistance dependent on silane functionalization is shown as a function of time in (b); the change in stripping voltage over time for HSE with 1 vol.-% functionalized and unfunctionalized LPS at 0.1 mA cm-2 and 80 °C is shown in (c); and the specific ionic conductivity of HSE and pure filler particles as a function of thiophosphate filler type (a=amorphous, c=crystalline) at a measurement temperature of 20 °C and a filler content of 1 vol.-% is shown in (d). Figure 7 Note: Ionic conductivity depends on the filler content of different active fillers (with and without functionalized LPS and argillium sulfide) and passivated filler particles (functionalized SiO2). All measurements were performed at 20°C. Figure 8 ((a), (b), (c)) Explanation: Functionalization reaction mechanism of LATP with CTMS and addition of particles to PEO (a), TGA analysis of raw and functionalized LATP particles (b), and FTIR data of raw and functionalized LATP particles (c). Figure 9 (a) and (b) Explanation: The ionic conductivity of PSE and HSE with different LATP contents and silane functionalization depending on the measurement temperature is shown in (a), and the ionic conductivity of PSE and HSE with different filler contents and functionalization depending on the measurement temperature of 20°C is shown in (b). Figure 10 (a) and (b) Explanation: SEM images of HSE with 10 vol.-% LATP at 9 k are shown in (a), and HSE with 10 vol.-% silane-functionalized LATP at 12.0 k resolution are shown in (b). Figure 11 ((a), (b), (c)) Explanation: For different particle size ranges, the ionic conductivity of HSE PEO-PEG with 10 vol.-% functionalized LATP at room temperature, depending on the crystallite size, is shown in (a), the ionic conductivity depending on the particle size and the maximum XRD peak intensity is shown in (b), and the particle surface before and after grinding at different crystallite sizes is shown in (c). Figure 12 Note: FTIR data for PEO-PEG PSE, PEO-PEG LATP, and PEO-PEG-LATP-CTMS HSE are displayed. (At 1055 cm⁻¹) -1 The signal is attributed to the ether groups of PEO and PEG, at 1095 cm⁻¹. -1 It exhibits CO,CC stretching and CC,CO stretching as well as CH2 rocking. The HSE with functionalized LATP is at 1104 cm⁻¹. -1 The additional peaks are attributed to the asymmetric stretching of Si-OC; Figure 13 Note: Exemplary Nyquist plots and equivalent circuits used for pure PEO-PEG and different HSEs; Figure 14 Note: Schematic diagram of solvent-based processes, including optional steps such as coating and battery construction; Figure 15 Note: Schematic diagram of the dry process, including optional steps such as calendering and cell fabrication; and Figure 16(a) and (b) Explanation: In (a), for the sample containing 10 vol.-% LATP, when considering the corresponding values ​​of silanized LATP filler particles and their non-functionalized counterparts, the ionic conductivity was observed to decrease from 0.014 mS / cm at 20 °C. -1 Strongly increased to 0.12 mS cm -1 In (b), studies determining residual porosity generally show that residual porosity is significantly reduced when the composite process is carried out in a dry manner.

[0122] In the overall multiple views, corresponding reference numerals denote corresponding parts. The examples set forth herein illustrate at least one embodiment of the invention, and these examples should not be construed as limiting the scope of the invention in any way. Detailed Implementation

[0123] Example Example 1: Material Preparation Initially, all materials used were dried in a vacuum (25 mbar) at 40°C for 4 hours. A solid polymer electrolyte for manufacturing polyethylene oxide (Mw = 900,000 g / mol) (Dow) was used at a Li / EO molar ratio of 1:14*, along with optional polyethylene glycol (Mw = 2,000 g / mol) (Sigma-Aldrich) and lithium salt bis(trifluoromethane)sulfonylimide (LiTFSI) (Clariant).

[0124] (*For PEO / PEG-based polymers, the conductive salt concentration is typically specified as the molar ratio of lithium from the conductive salt to the repeating ethylene oxide (=EO) unit in the polymer).

[0125] Various filler particles are added, each with different material properties, as shown in the table below. Table 1: Properties of different filler particles.

[0126] For thiophosphate filler particles, the filler content varied between 0.5 and 2.5 vol.-%, and for oxide filler particles, the filler content varied between 5 and 15 vol.-%.

[0127] Example 2: HSE mixture of thiophosphates Under an argon atmosphere, thiophosphate filler particles were dispersed in acetonitrile (ACN) in a glove box. A suspension settling step of 0 to 24 hours was applied prior to the subsequent dissolution step. For further processing, the suspension was transferred to a drying chamber (20°C ambient temperature, dew point -45°C). For the silane-containing mixed solid electrolyte (HSE), (chloromethyl)(phenethyl)trimethoxysilane (CTMS) was added to the ACN-thiophosphate filler suspension and stirred at 60°C for 1 hour using a magnetic stirrer. Subsequently, a polymer (PEO:PEG ratio of 80:20 wt.-%) and LiTFSI were added to the suspension and homogenized using a 40 mm toothed disk dissolver (DISPERMAT LC, VMA-Getzmann GmbH, Germany).

[0128] Initially, a rotation speed of 2000 rpm was applied, and after 5 minutes, the speed was increased to 5000 rpm and maintained for 25 minutes. The effect of energy input during the dispersion step was investigated for PEO-PEG-LiTFSI PSE with 1 vol.-% LPS. Therefore, in addition to a dissolver, a magnetic stirrer and a shaker were used to dissolve and disperse PEO, PEG, LiTFSI, and LPS.

[0129] Subsequently, using a coater equipped with a scraper (ZAA2300 from Zehntner Testing Instruments, Switzerland), the coating was applied at a hot plate temperature of 30°C and a thickness of 5 mm / s. -1 At a high speed, the solution is applied directly to the non-adhesive release foil or after standing for 24 hours. To create a separator of sufficient thickness (approximately 80 µm) for processing, three layers are applied on top of each other, with each layer drying for 10 minutes. Finally, the coater is heated to 80°C to melt the individual separator layers.

[0130] When the suspension was stored for 24 hours after the dispersion step, the ionic conductivity increased slightly. This increase in conductivity was attributed to the degassing of the suspension, as the equipment could not apply a vacuum. Prior to the dispersion step with PEO / PEG and LiTFSI, the conductivity increased significantly when LPS was dispersed in ACN for 24 hours. This increase in conductivity can be explained by the visible blue color change of the solution due to ligand formation. The LPS may have been completely dispersed in acetonitrile as a solvent in the form of primary particles. It is highly likely that no aggregates were present.

[0131] Therefore, for all further experiments, the thiophosphate particles were dispersed in ACN for 24 hours to ensure sufficient time for ligand formation. If the suspension was allowed to stand for 24 hours after the dissolution step, no additional increase was observed, but a slight decrease in conductivity was observed. This may be attributed to the sedimentation and aggregation effects of the LPS particles. Immediately following the process time, the effect of stress intensity during the dispersion step was investigated. Figure 1 b). Regarding the ionic conductivity and residual porosity of the resulting HSE, processes using a shaker, a magnetic stirrer with an agitator, and a dissolver were compared.

[0132] As stress intensity increases, porosity decreases and an increase in ionic conductivity is observed, as the thiophosphate particles and LiTFSI are more uniformly distributed in the polymer matrix.

[0133] Therefore, the dissolver was used for all further experiments.

[0134] The effect of the filler content of thiophosphate particles on the ionic conductivity of HSE was then investigated. Membranes with LPS contents ranging from 0 vol.% to up to 2.5 vol.% were fabricated and analyzed by EIS.

[0135] With increasing LPS content, conductivity decreased. These results indicate that LPS particles act as a barrier to ion transport, rather than providing a rapid transport pathway. Furthermore, for suspensions containing LPS, the deposited material was observed to improve upon Raman spectroscopy analysis. Figure 2 b). The spectrum shows the typical peak of pure sulfur, at 217 cm⁻¹. -1 For SSS bending, at 472cm -1 The SS stretching indicates that sulfur precipitates upon the addition of PEO-PEG and LiTFSI. Most likely, the sulfur particles impede ion transport. Figure 3 a) It also reduced the overall ionic conductivity of the HSE. To reduce the interfacial resistance between the filler particles and the polymer solid electrolyte (PSE) and to improve the stability of LPS particles in the HSE, the chemical bonding of organic and inorganic materials was investigated.

[0136] For functionalized LPS particles, the transport path may be shortened along the interface (2) or even through the filler particles (3), such as Figure 3 As described in b.

[0137] LPS particles are functionalized using silanes (CTMS) bonded to (chloromethyl)(phenylethyl)trimethoxy groups. Figure 4The reaction mechanism was explained, demonstrating that CTMS interacts chemically with the LPS surface via Si-S bonds. Different types of bonding with the particle surface are possible, such as single chemical bonds, up to three chemical bonds, or the formation of monolayers and multilayers.

[0138] To verify the successful functionalization of LPS particles with CTMS, thermogravimetric analysis (TGA) measurements were performed on both the original and functionalized particles. Figure 4 b).

[0139] Since the mass loss below 200°C corresponds to physically absorbed water and varies for each sample, the TGA curves were normalized to values ​​recorded at 200°C. A significant increase in mass loss of 8.37% was observed for the functionalized LPS particles compared to the original LPS particles. This result indicates that CTMS was successfully grafted onto the LPS surface via covalent bonding.

[0140] During subsequent HSE production, no deposited material was observed in suspensions containing functionalized LPS particles. Furthermore, for HSE containing 1 vol.% functionalized LPS particles, the residual porosity decreased significantly from 8.2% to 0.35%. Figure 2 c). As a result, the ionic conductivity (RT) at room temperature increased from 1.4 × 10⁻⁶ for pure PSE. -5 S cm -1 The HSE significantly increased to 6.2% with the incorporation of 1 vol.% functionalized LPS particles. -5 S cm -1 ( Figure 2 d).

[0141] Furthermore, the lithium-ion transference numbers in PEO PSE, PEG-PEG PSE, and HSE with functionalized LPS particles were determined to be 0.12, 0.52, and 0.55, respectively. Due to the increased lithium-ion transference number, the functionalized LPS particles may participate in lithium-ion transport. Therefore, the covalent bonding of silane to the particle surface leads to a reduction in the interfacial resistance between the LPS particles and the PSE, thereby accelerating the transport pathway through the solid electrolyte. Scanning electron microscopy (SEM) images of films with and without silane bonding are shown... Figure 5 In addition to affecting the LPS interface, silane also affects the PSE. In samples without silane, the grain boundaries between PEG and PEO are visible, which is suppressed by the addition of silane. Furthermore, the functionalized LPS particles are more uniformly distributed.

[0142] Therefore, the addition of silane not only affects the interface between LPS and PSE, but also stabilizes the LPS particles within the PEO-PEG matrix, thus minimizing aggregation and suppressing sulfur formation. For HSE with functionalized filler particles, significantly lower cluster size and cluster size deviation were observed.

[0143] In the processing of LPS blends, H2S formation plays a crucial role in safety. Therefore, the effects of chemical bonding and the resulting embedding of LPS particles into the PSE phase on H2S formation were investigated. Figure 6 The study shows H2S formation dependent on exposure time to ambient air. For HSE without silane, H2S was formed within the first 20 minutes, while no H2S was detected for HSE with silane functionalization. These results indicate that the safety of handling HSE can be significantly improved through silane bonding. However, another challenge is the instability of LPS to lithium metal, as pure lithium anodes should be used to provide high energy density. To investigate whether embedding LPS particles through silane functionalization can improve the stability of this anode material, the interfacial resistance of symmetric Li-HSE-Li cells with and without silane was measured via EIS.

[0144] like Figure 6 As shown in b, through silane functionalization, the interfacial resistance is significantly reduced and remains constant. The HSE with silane shows an interfacial resistance of approximately 60 Ω, compared to the HSE without silane, starting at 300 Ω, rising to as high as 500 Ω after one week, and increasing to 4000-5000 Ω after one month. Secondly, for lithium metal symmetric cells, when at 0.1 mA / cm²... 2 During the stripping-electroplating experiment at 80°C and at the specified current density, a constant voltage was obtained for the HSE with functionalized LPS particles, while for the non-functionalized particles, a sharp increase in voltage over time was observed, reaching up to 0.5 V. After 190 h, the non-functionalized battery exhibited a large voltage drop due to short circuit. If the LPS is in direct contact with the lithium metal electrode, the voltage increase is attributed to stability issues. After a slight increase in overpotential at the beginning (40 mV), a low polarization voltage (3 mV) was observed for the HSE with functionalized LPS. Functionalization suppresses direct contact between the LPS particles and the lithium metal interface, thereby improving cycle stability.

[0145] In summary, the ionic conductivity, lithium-ion transference number, and chemical stability to lithium and ambient air of HSE with added LPS particles can be significantly improved by functionalizing LPS particles with silanes. This also applies to the chemical stability of suspensions formulated in the HSE manufacturing process.

[0146] Furthermore, the influence of thiophosphate properties on the ionic conductivity of HSE was investigated. Therefore, three LPS materials with different intrinsic conductivity and particle sizes, as well as one sulforaphane-germanium ore material, were used as fillers. The properties of the thiophosphates are shown in Table 1 of the experimental section. The specific ionic conductivity of HSE with silane and different thiophosphates, and the ionic conductivity of the filler particles, are shown as follows. Figure 6 As depicted by d, submicron and micron LPS exhibit similar HSE ionic conductivity, while for amorphous LPS, the HSE ionic conductivity decreases slightly. The highest HSE ionic conductivity, 0.74 mS / cm, is achieved in the argentite-germanium sulfide material. -1 The relatively increased ionic conductivity of HSEs with sulfide-germanium sulfide filler particles indicates that the intrinsic ionic conductivity of the filler particles directly affects the ionic conductivity of the HSE. Besides the increased transfer number, this observation also implies that the participation of active filler particles promotes lithium-ion transport. Secondly, the filler particle structure shows its influence on the resulting HSE ionic conductivity. Micron-sized amorphous LPS filler particles, while having similar particle sizes to crystalline LPS particles, exhibit slightly higher ionic conductivity. However, compared to amorphous LPS filler particles, crystalline filler particles lead to enhanced transport properties in the HSE. However, for pure sulfide solid electrolyte (SE) layers, the use of amorphous LPS particles improves the contact between sulfide particle interfaces, thereby increasing the overall SE ionic conductivity, despite the higher intrinsic ionic conductivity of the crystalline LPS phase. These findings suggest that the surface of the filler particles plays a role in promoting lithium-ion transport. Therefore, optimizing the application of LPS materials as fillers in HSEs requires different surface modifications than those required for pure inorganic solid electrolytes.

[0147] For micron- and submicron-sized LPS, similar HSE ionic conductivity was achieved despite significant differences in particle size. Although the ionic conductivity of the filler particles was within the same range, significant differences were expected because using submicron filler particles would reduce crystallinity through localized variations within the polymer structure, thereby increasing the ionic conductivity of PSE. Therefore, submicron particle size should be beneficial, as it also reduces the crystalline phase of the polymer if a uniform particle distribution is achieved. However, no increase in HSE ionic conductivity was observed through the use of submicron particles. Overall, the highest ionic conductivity was obtained with 1 vol.% micron-sized silver-germanium sulfide filler particles.

[0148] As mentioned above, for submicron LPS, increasing the filler content to as high as 2.5 vol.-% does not further improve the ionic conductivity of HSE, possibly due to the difficulty in achieving a uniform distribution of LPS submicron particles. Therefore, for argyrocerium sulfide materials with an x50 of 3 µm, attempts were made to reduce the risk of filler particle aggregation at 2.5 vol.-%. Therefore, increased filler content was investigated for argyrocerium sulfide materials and compared with LPS HSE and HSE with passivated SiO2 filler, such as... Figure 7 As shown.

[0149] As the filler content increases, the conductivity of LPS without the functionalization described above decreases. Figure 2 A comparison of functionalized passivated and active filler particles showed that adding passivated filler particles did not improve conductivity.

[0150] Therefore, the improvement in ionic conductivity, as seen in the SEM images shown above, can be ruled out as being due to changes in the polymer structure caused by silane (CTMS) or the inhibitory interfacial effects between PEO and PEG. In contrast, for HSE containing silylgermanium sulfide filler, ionic conductivity increases with increasing filler content, up to 0.1 mS cm⁻¹. However, for higher filler contents of 2.5 vol.-%, the ionic conductivity of submicron LPS decreases. Sufficient homogenization cannot be achieved for the process route already used at 2.5 vol.-%, highlighting the importance of the selected filler particle size and the resulting distribution. With process adjustments, higher filler contents for submicron particles can lead to a further increase in ionic conductivity.

[0151] Figure 1-7 The results are further described in the text.

[0152] Example 3: Oxide Mixed HSE For oxide-based HSE, the effect of a pre-grinding step on LATP filler particles was evaluated and compared with that of raw LATP particles. For both options, LATP particles (SCHOTT AG, Germany) were dispersed in isopropanol (IPA). Grinding was performed in a planetary ball mill (PULVERISETTE 7, FRITSCH GmbH, Germany) with an 80 ml grinding bowl and ZrO2 grinding media with a diameter of 1 mm and a solids content of 20 wt.-% LATP in IPA. The grinding time was set to 25 minutes at a rotation speed of 400 rpm. Furthermore, different grinding conditions were applied for variations in LATP particle size. For three different rotation speeds of 200, 400, and 600 rpm and a solids content of 10 wt.-%, the grinding time varied between 2 and 60 minutes. For further processing, the suspension was transferred to a drying chamber (at an ambient temperature of 20°C and a dew point of -45°C). For silane-containing HSE, CTMS was added to the suspension and stirred at 60°C for 1 hour using a magnetic stirrer. For further processing of ACN, a polymer (PEO:PEG 80:20 wt.-%) and LiTFSI were added and dissolved using a 40 mm toothed disc (DISPERMAT LC from VMA-Getzmann GmbH, Germany). An initial rotation speed of 2000 rpm was applied, increasing to 5000 rpm after 5 minutes and maintaining this speed for 25 minutes. For thiophosphate HSE, coating was performed using the above process parameters.

[0153] To explore the potential transfer of silane functionalization to oxide filler particles, functionalized LATP was compared with non-functionalized LATP and functionalized SiO2 as passivation fillers. Furthermore, for functionalized LATP, various filler contents were studied and characterized by EIS.

[0154] To verify the functionalization of LATP particles, Fourier transform infrared spectroscopy (FTIR) and TGA measurements were performed. Secondly, the reaction mechanism is as follows: Figure 8 The description.

[0155] Although no significant mass loss was observed in the pristine LATP, a 6.14% mass reduction was detected in the functionalized LATP particles. This was due to the expectation of no residual silane in the sample after repeated washing of the LATP particles in isopropanol (IPA), leading to the assumption that CTMS covalently bonded to the particle surface. Therefore, the TGA data indicate successful grafting of the LATP particles. FTIR analysis of the pristine and functionalized LATP particles showed a mass reduction in the range of 500–600 cm⁻¹. -1 The asymmetric bending vibration of OPO and the overlapping tensile vibration of Ti-O, and the vibration at 800 to 1200 cm⁻¹ -1Symmetric tensile vibration of the PO bond.

[0156] For functionalized LATP particles, from 927 cm -1 Up to 980 cm -1 to 800 to 1200 cm -1 The displacement of the symmetric tensile vibration of the PO bond at 980 cm is visible, which may be attributed to the displacement at 980 cm. -1 The new peak attributed to the Si-O bond further confirms the successful grafting of LATP particles with CTMS. A chemical bond may exist between CTMS and PEO or PEG, but this cannot be proven because only a small amount of PEO could react with silane, and the minute shifts within the Si-C peak cannot be resolved by HSE FTIR analysis.

[0157] However, the polarity and thus compatibility of the LATP particles with the polymer are altered. As has been observed with thiophosphate filler particles, the addition of nonfunctionalized LATP does not improve the ionic conductivity of the HSE. Since LATP is not sintered in the HSE, high resistance between LATP particles can be expected. The nonfunctionalized LATP particles form clusters, resulting in a non-uniform LATP distribution. Figure 10 a) and the LATP cluster pathway did not provide faster ion transport. On the other hand, the chemical bonds formed between the polymer and the active filler particles via silanization led to an increase in the ionic conductivity of HSE. The highest ionic conductivity of 0.048 mS / cm was obtained at 10 vol.-%. -1 For functionalized LATP, the ionic conductivity is expected to increase further with increasing filler content until LATP-LATP contact occurs. However, as discussed for thiophosphate filler particles, the occurrence of filler particle contact also depends on particle size and dispersion. For functionalized LATP filler particles with a particle size x50 of 0.085 μm, as... Figure 10 The SEM image of the cross section in b depicts a level of homogenization up to 10 vol.-%.

[0158] To investigate whether active filler particles are necessary for obtaining a significant increase in ionic conductivity, the effect of adding 10 vol.% functionalized passivating filler was studied. At a measurement temperature of 20 °C, an increase in ionic conductivity from 0.014 mS / cm was observed. -1 Slightly increased to 0.026 mS cm -1 However, as Figure 9As shown in b, the use of functionalized active filler particles significantly improved the ionic conductivity of the HSE. Furthermore, compared to the 0.52 transport number of PEO-PEG-PSE, the transport number of the HSE using functionalized LATP was determined to be 0.576, supporting the hypothesis that the active filler particles participate in lithium-ion transport. To clarify whether lithium ions are transported along the filler particle interface or through the particle volume for the HSE with functionalized LATP, the LATP particle size was varied.

[0159] Therefore, LATP particles were ground to various particle sizes using wet media milling. X-ray diffraction measurements were performed to investigate structural changes during milling. Decreased LATP particle size and crystallinity led to a decrease in peak intensity. As observed in the XRD measurements, a decrease in peak intensity was observed with increasing milling speed and stress intensity. Therefore, depending on the milling conditions, not only the filler particle size but also the crystallinity and grain size can change. Due to the structural changes in LATP particles, it is impossible to consider only the correlation between ionic conductivity and particle size. Furthermore, the crystallite size determined by XRD measurements must also be considered. Therefore, for a filler content of 10 vol.-%, for two different particle size ranges, the ionic conductivity depends on the crystallite size (…). Figure 11 a). Furthermore, ionic conductivity exhibits a function of particle size and crystallite size ( Figure 11 b).

[0160] For similar LATP particle sizes, ionic conductivity decreases with decreasing crystallite size. For a particle size range of 0.085 to 0.14 μm, ionic conductivity reaches 0.026 to 0.048 mS / cm with increasing crystallite size. -1 This indicates that the LATP particle structure has a strong influence on ion transport in HSE. For example... Figure 11 As described in b, the effect of the structural change in LATP particles on the increase in conductivity is evident as the particle size increases with the increase in crystallite size. Furthermore, for x50 values ​​of 1.69 μm and 0.78 μm, the reduced LATP particle size leads to an increase in ionic conductivity from 0.035 mS / cm. -1 Increased to 0.056 mS cm -1 As the LATP particle size further decreased to 0.1 μm with a x50 value, a stronger structural change occurred, and a particle size of 0.026 mS / cm was obtained. -1The surface conductivity of LATP particles influences the ionic conductivity of HSE, indicating that the LATP particle surface is involved in lithium-ion transport. This effect reveals the necessity of a suitable filler particle design with high crystallinity and crystallite size on the surface, as opposed to the application of pure oxide SE, where crystallinity and grain size are increased through the final sintering step. The significant effect of particle size can only be studied when the filler particles exhibit the same structural properties. These changes cannot be completely suppressed due to the stress applied during grinding. A slight reduction in LATP particle size enhances performance; therefore, grinding should be performed under relatively mild conditions, such as low rotational speeds. Higher speeds result in greater stress intensity and a greater number of stress events. It can be noted that the reduction in particle size occurs immediately at all speeds, while at low speeds, the crystallite size decreases after sufficient time and a sufficient number of stress events, allowing for particle size reduction under mild conditions without excessive alteration of the crystallinity.

[0161] Figure 8 The results are further described in section 11.

[0162] Example 4: Dry process for HSE production The entire process chain of dry processes used in HSE production is in Figure 15 As shown in the diagram, firstly, LATP packing particles were dispersed in isopropanol (IPA) in a drying chamber (dew point of -45°C at an ambient temperature of 20°C). A mixed solid electrolyte (HSE) containing silane (chloromethyl)(phenylethyl)trimethoxysilane (CTMS) was added to the LATP-IPA packing suspension, and the mixture was stirred at 60°C for 1 hour using a magnetic stirrer.

[0163] Simultaneously, to homogenize the PEO-PEG-LiTFSI powder mixture, all materials were premixed in a drum mixer (WAB Turbula T2F) at 49 rpm. In the first step, PEO and PEG were mixed for 15 minutes. In the second step, the conductive salt was added and mixed again for 15 minutes to obtain a uniformly distributed composition. For further processing, the powder mixture from the drum mixer was additionally processed in a kneader (ThermoFisher HAAKE PolyLab Rheomix 610). For this purpose, the processing chamber was heated to 60°C. During the filling stage, the rotation speed was set to 5 rpm, and the powder mixture was inserted to achieve a volume filler content of 30-50%.

[0164] After the polymer electrolyte component is added, the LATP-IPA-CMPhTMS particle suspension is added slowly and continuously, ensuring the solvent component evaporates. Once this process is complete, the rotation speed is increased to 60 rpm at a slope of 27 rpm / min. The total kneading time after the filling stage is 10 minutes.

[0165] To analyze ionic conductivity, the molten mixed electrolyte was removed from the kneader and calendered (using a laboratory calender from Saueressig). The calender rolls were heated to 120°C, and the circumferential speed was set to 0.2 m / min. The gap between the two rolls was controlled to obtain a free-standing mixed electrolyte layer with a thickness of approximately 500 μm. Subsequently, a perforator was used to obtain mixed electrolyte discs with a diameter of 16 mm.

[0166] To investigate whether active filler particles are necessary for achieving a significant increase in ionic conductivity, the effects of adding different amounts of functionalized passivating filler materials were studied. For example... Figure 16 As shown in a), for samples containing 10 vol.-% LATP, when considering the corresponding values ​​of silanized LATP filler particles relative to their nonfunctionalized counterparts, the ionic conductivity was observed to increase from 0.014 mS / cm at 20 °C. -1 The strength increased to 0.12 mS cm. -1 .like Figure 16 As shown in b), studies determining residual porosity generally indicate a significant decrease when the composite process is carried out under dry conditions. In the latter case, an increase in the silane content in the formulation leads to a further, slight reduction.

[0167] Example 5: Grinding Details For grinding, LATP particles (SCHOTT AG, Germany) were first dispersed in isopropanol (IPA). Grinding was carried out in a planetary ball mill (PULVERISETTE 7, FRITSCH GmbH, Germany), with a grinding bowl volume of 80 ml, using ZrO2 grinding media with a diameter of 1 mm and a solids content of 20 wt.-% LATP in IPA. The grinding time was set to 25 minutes at a rotation speed of 400 rpm. Furthermore, different grinding conditions were applied for variations in LATP particle size. For three different rotation speeds of 200, 400, and 600 rpm and a solids content of 10 wt.-%, the grinding time varied between 2 and 60 minutes.

[0168] The grinding parameters, as well as the resulting particle size and crystallite size, were measured and are disclosed in Table 2 below. Table 2: Grinding parameters and resulting particle and crystallite sizes.

[0169] Example 6: Characterization Experiment Based on theoretical and measured densities, the porosity of the manufactured membrane is calculated using the separator mass m, sample volume V, initial density ᵢ, and the weight content xi of individual components. in .

[0170] To determine the H2S content released from the mixed electrolyte, release tests were performed on membranes containing 1 vol.-% LPS, with and without CTMS, under normal and dry chamber atmospheres. For this purpose, 1 g of sample was placed in a desiccator, and the hydrogen sulfide content was manually determined over 90 minutes using an H2S sensor X-am 5000 (Dräger GmbH, Germany). A ventilator was placed in the desiccator to ensure uniform air distribution.

[0171] Using a sample mass of 1 g and a volume of 18,500 ml, the amount of H2S released (cm³) can be determined. 3 g -1 ).

[0172] Raman spectroscopy (using an XR 2 Raman microscope from Thermo Scientific, USA) was used to determine the composition of the precipitated material in the suspension. Therefore, the material was applied to a slide and sealed. Measurements were performed at a wavelength of 532 nm and a power of 1 mW. Each measurement was performed three times, with an exposure time of 60 seconds.

[0173] To verify functionalization, thermogravimetric analysis (TGA) was performed on both functionalized and pristine LATP and LPS particles at a heating rate of 10 kJ / min under a nitrogen atmosphere, ranging from 25 to 950 °C (TGA / DSC 1 sTARe from Mettler-Toledo GmbH, Griffin, Switzerland). The chemical bonds of pristine and functionalized LATP particles, as well as PSE and HSE, were analyzed by Fourier transform infrared spectroscopy (FTIR, VERTEX 70, Bruker). To remove residual silane not bonded to the particle surface prior to TGA and FTIR analysis, three washing steps were applied, using IPA for LATP and heptane for LPS.

[0174] As described by Wiegmann and Helmers et al., ionic resistance was measured by potentiostatic electrochemical impedance spectroscopy (EIS) (ZENNIUM, Zahner GmbH, Germany) using blocking conditions and different measurement temperatures ranging from 20 to 80 °C. The resulting Nyquist plots and equivalent circuits for pure PSE and different HSE types were plotted.

[0175] The specific ionic conductivity is calculated using the following equation, based on the ionic resistance Rion, the separator thickness δ, and the electrochemical active area A: .

[0176] In a copper-lithium-separator-lithium-copper coin cell, the stability of the separator to lithium is studied by measuring the interfacial resistance, which depends on the storage time, via EIS.

[0177] The battery was heated to 80°C once to ensure adequate contact between the lithium foil and the separator. Resistance was measured periodically at monthly intervals at a measurement temperature of 20°C. Cycling of the symmetric lithium battery was performed at 0.1 mA cm⁻², with 1 hour of stripping and electroplating each time, and a measurement temperature of 80°C. The mobility number in the symmetric lithium battery was determined via the Bruce-Vincent method using a combination of EIS measurements and 10 mV DC polarization.

[0178] Cross-sections of the diaphragm were prepared using wide ion beam (BIB) technology with an IM5000 “ArBlade”. Subsequently, scanning electron microscopy (SEM) images of the cross-sections (Hitachi High Tech SU5000) were recorded to analyze the packing particle distribution.

[0179] To determine the crystallite size of the LATP particles, X-ray diffraction (XRD) measurements were performed using Cu-Kα radiation (Panalytical's Empyrean) at a wavelength of 0.154 nm, with a 2θ range from 20 to 90° and a step size of 0.053°. The XRD data were analyzed using the Williamson-Hall method with Highscore Plus software to determine the crystallite size.

[0180] Although the invention has been described with respect to at least one embodiment, further modifications are possible within the spirit and scope of this disclosure. Therefore, this application is intended to cover any variations, uses, or modifications of the invention using its general principles. Furthermore, this application is intended to cover any deviations from this disclosure that fall within the limitations of the appended claims and are known or conventionally practiced in the field to which this invention pertains.

Claims

1. A process for producing mixed solid electrolytes (HSEs) based on solvents, comprising the following steps: a) Provide a suspension of filler particles (FP) in a solvent. b) Provide a mixture of PEO, PEG, and lithium conductive salt in a solvent. c) Disperse the filler particle suspension from step a) in the mixture of PEO, PEG, and lithium conductive salt from step b). d) Optionally, the resulting mixture is degassed. e) Remove the solvent. f) Thus, a mixed solid electrolyte (HSE) is obtained.

2. The process according to claim 1, wherein the HSE is further homogenized and / or processed by other means, such as kneading, layering, coating and / or extrusion.

3. The process according to claim 1 or 2, wherein the filler particles (FP) are thiophosphate and / or oxide filler particles.

4. The process according to any one of the preceding claims, wherein the particles are made of particles having the general formula Li x MeO y The material composition is given by y = (x + n) / 2, where 0 ≤ x ≤ 3, and Me is selected from metals with a valence of n, P or B, where n is 3, 4 or 5.

5. The process according to any one of the preceding claims, wherein the particles are composed of a material having a garnet-like crystal phase, the material having the empirical formula: Li 7+x-y M x II M 3-x III M 2-y IV M y V O 12 M II It is a divalent cation, M III It is a trivalent cation, M IV It is a tetravalent cation, M V It is a pentavalent cation, and 0≤x<3 and 0≤y<2, or a compound derived therefrom.

6. The process according to any one of the preceding claims, wherein the particles are composed of a material having a crystalline phase isomorphic to NaSICon, said material having the empirical formula: Li 1+x-y M 5+y M 3+x M 4+2-x-y (PO4)3, where x and y are in the range from 0 to 1 and (1+xy)>1, and M is a cation with a valence of +3, +4 or +5, or a compound derived therefrom.

7. The process according to any one of the preceding claims, wherein the filler particles are selected from the group consisting of lithium lanthanum tantalum zirconium oxide (LLZTO), lithium lanthanum zirconium oxide (LLZO), lithium lanthanum titanium oxide (LLTO), lithium superionic phosphorus sulfide (LSPS), lithium garnet phosphorus sulfide (LGPS), lithium phosphorus sulfide (LPS), lithium phosphorus sulfide (LPSCl), lithium aluminum titanium phosphate (LATP), lithium garnet solids (LGS), and / or mixtures thereof.

8. The process according to any one of the preceding claims, wherein the lithium conductive salt is selected from LiAsF6, LiClO4, LiSbF6, LiPtCl6, LiAlCl4, LiGaCl4, LiSCN, LiAlO4, LiCF3CF2SO3, Li(CF3)SO3 (LiTf), LiC(SO2CF3)3, LiPF6, LiPF3(CF3)3 (LiFAP), LiPF4(C2O4) (LiTFOB), LiBF4, LiB(C2O4)2 (LiBOB), LiBF2(C2O4) (LiDFOB), LiB(C2O4)(C3O4) (LiMOB), Li(C2F5BF3) (LiFAB), Li2B 12 F 12 The group consisting of (LiDFB), LiN(FSO2)2 (LiFSI), LiN(SO2CF3)2 (LiTFSI), LiN(SO2C2F5)2 (LiBETI)LiClO4, lithium bis(oxalate)borate, lithium difluoro(oxalate)borate, LiSO3CF3, lithium 2-pentafluoroethoxy-1,1,2,2-tetrafluoroethanesulfonate, lithium 2-pentafluoroethoxy-1,1,2,2-tetrafluoroethanesulfonate (LiSO3C2F4OC2F5), and / or mixtures thereof.

9. The process according to any one of the preceding claims, wherein step a) comprises grinding the filler particles.

10. The process according to claim 9, wherein the grinding is performed by wet grinding.

11. The process according to claim 9 or 10, wherein the milling is carried out in a solvent selected from the group consisting of alcohols (especially ethanol, isopropanol, 1-propanol or butanol), ketones (especially acetone or methyl ethyl ketone), acetonitrile, N-methyl-1-pyrrolidone (NMP), N,N-dimethylacetamide or dimethyl carbonate and / or mixtures thereof.

12. The process according to any one of claims 9 to 11, wherein optionally, the milled mixture is subjected to a drying step in a drying chamber until the filler particles are dry and the solvent content is less than 1 wt.

13. The process according to any one of the preceding claims, wherein step a) comprises silanizing the filler particles with silane.

14. The process according to claim 13, wherein the silane is based on one of the following formulas: (X2)nSi(R1-X1)4-n or (X2)nSi(R1-X1)m(R2)4-(m+n), The silane has at least one silicon atom, which carries one to three leaving groups X1 (e.g., alkoxy, acyloxy, Br-, I-, Cl- or H- atoms, toluenesulfonyl or trifluoromethanesulfonyl) as reactive groups.

15. The process according to any one of claims 13 or 14, wherein the silanization is performed after grinding the filler particles.

16. The process according to any one of claims 13 to 15, wherein the silanization is performed at a temperature between 50°C and 70°C, optionally about 60°C.

17. The process according to any one of claims 13 to 16, wherein the silanization is carried out at room temperature in the presence of a catalyst.

18. The process according to any one of claims 13 to 17, wherein the silanization is carried out under stirring.

19. The process according to any one of the preceding claims, wherein the solvent used is selected from the group consisting of acetonitrile (ACN), alcohols (especially ethanol, isopropanol, 1-propanol or butanol), ketones (especially acetone or methyl ethyl ketone), N-methyl-1-pyrrolidone (NMP), N,N-dimethylacetamide and dimethyl carbonate and mixtures thereof.

20. The process according to any one of the preceding claims, wherein dispersion c) is promoted by using a device selected from shaker, magnetic stirrer (optionally with agitator), rotor-stator disperser, ultrasonic disperser, high-pressure homogenizer, dissolver, and combinations thereof.

21. The process according to any one of the preceding claims, wherein the PEO:PEG ratio of the PEO:PEG mixture in step b) is between 3:1 wt.-% and 5:1 wt.-%, and optionally the PEO:PEG ratio is about 4:1 wt.-%.

22. The process according to any one of the preceding claims, wherein the dispersing apparatus for step c) is selected from the group consisting of a rocking plate, a magnetic stirrer (optionally with an agitator) and a dissolver.

23. The process according to any one of the preceding claims, wherein the degassing step is performed in a vacuum chamber at a pressure of about 1000 Pa or lower.

24. The process according to any one of the preceding claims, further comprising an additional step in which the HSE is coated on a surface and / or calendered and / or passed through a kneader, extruder or three-roll mill.

25. A process for the dry production of mixed solid electrolytes (HSE), comprising the following steps: a) Provide a suspension of filler particles (FP) in a solvent. b) PEO, PEG, and lithium-ion conductive salt in dry powder form are added simultaneously or sequentially to the mixed aggregate. c) Continuously dispersing and / or mixing the particulate suspension obtained in step a) within the mixed aggregates. d) Thus, a mixed solid electrolyte (HSE) is obtained.

26. The process according to claim 25, wherein the filler particles (FP) are thiophosphate and / or oxide filler particles.

27. The process according to claim 25, wherein the particles are composed of particles having the general formula Li x MeO y The material composition is given by y = (x + n) / 2, where 0 ≤ x ≤ 3, Me is selected from metals with a valence of n, P or B, where n is 3, 4 or 5.

28. The process of claim 25, wherein the particles are composed of a material having a garnet-like crystal phase, the material having the empirical formula: Li 7+x-y M x II M 3-x III M 2-y IV M y V O 12 M II It is a divalent cation, M III It is a trivalent cation, M IV It is a tetravalent cation, M V It is a pentavalent cation, and 0≤x<3 and 0≤y<2, or a compound derived therefrom.

29. The process of claim 25, wherein the particles are composed of a material having a crystalline phase isomorphic to NaSICon, the material having the empirical formula: Li 1+x-y M 5+y M 3+x M 4+2-x-y (PO4)3, where x and y are in the range from 0 to 1 and (1+xy)>1, and M is a cation with a valence of +3, +4 or +5, or a compound derived therefrom.

30. The process according to claim 25, wherein the filler particles are selected from the group consisting of lithium lanthanum tantalum zirconate (LLZTO), lithium lanthanum zirconate (LLZO), lithium lanthanum titanate oxide (LLTO), lithium superionic phosphorus sulfide (LSPS), lithium garnet phosphorus sulfide (LGPS), lithium phosphorus sulfide (LPS), lithium phosphorus sulfide (LPSCl), lithium aluminum titanium phosphate (LATP), lithium garnet solids (LGS), and / or mixtures thereof.

31. The process according to any one of claims 25 to 30, wherein step a) comprises grinding the filler particles.

32. The process according to claim 31, wherein the grinding is performed by wet grinding.

33. The process according to claim 31 or 32, wherein the milling is carried out for 2 to 60 minutes at a rotational speed between 100 and 600 rpm and a solid content between 5 and 20 wt.%, optionally until the particle size is 1 μm in diameter or smaller.

34. The process according to any one of claims 31 to 33, wherein the milling is carried out in a solvent selected from the group consisting of alcohols (especially ethanol, isopropanol, 1-propanol or butanol), ketones (especially acetone or methyl ethyl ketone), acetonitrile, N-methyl-1-pyrrolidone (NMP), N,N-dimethylacetamide or dimethyl carbonate and / or mixtures thereof.

35. The process according to any one of claims 31 to 34, wherein optionally, the milled mixture is subjected to a drying step in a drying chamber until the filler particles are dry and the solvent content is less than 1 wt.

36. The process according to any one of claims 25 to 30, wherein step a) comprises silanizing the filler particles with silane.

37. The process of claim 36, wherein step a) comprises silanizing the filler particles using a silane according to one of the following formulas: (X2)nSi(R1-X1)4-n or (X2)nSi(R1-X1)m(R2)4-(m+n), The silane has at least one silicon atom, which carries one to three leaving groups X1 (e.g., alkoxy, acyloxy, Cl- or H- atoms) as reactive groups.

38. The process according to claim 37, wherein the siloxane is selected from the group consisting of (chloromethyl)(phenylethyl)trimethoxysilane (CTMS) and / or chloropropyltrimethoxysilane, and combinations thereof.

39. The process of claim 36, wherein the silanization is performed after grinding the filler particles.

40. The process of claim 39, wherein the silanization is performed between 50°C and 200°C, between 50°C and 180°C, between 50°C and 150°C, between 50°C and 100°C, between 50°C and 70°C, or optionally at a temperature of about 60°C.

41. The process according to claim 39, wherein the silanization is carried out at room temperature (20°C) in the presence of a catalyst.

42. The process according to claim 39, wherein the silanization is carried out under stirring.

43. The process according to any one of claims 25 to 42, wherein the PEO:PEG ratio of the PEO:PEG mixture in step b) is between 3:1 wt.-% and 5:1 wt.-%, and optionally the PEO:PEG ratio is about 4:1 wt.-%.

44. The process according to any one of claims 25 to 43, wherein the lithium-ion conductive salt in step c) is selected from LiAsF6, LiClO4, LiSbF6, LiPtCl6, LiAlCl4, LiGaCl4, LiSCN, LiAlO4, LiCF3CF2SO3, Li(CF3)SO3 (LiTf), LiC(SO2CF3)3, LiPF6, LiPF3(CF3)3 (LiFAP), LiPF4(C2O4) (LiTFOB), LiBF4, LiB(C2O4)2 (LiBOB), LiBF2(C2O4) (LiDFOB), LiB(C2O4)(C3O4)(LiMOB), Li(C2F5BF3) (LiFAB), Li2B 12 F 12 The group consisting of (LiDFB), LiN(FSO2)2 (LiFSI), LiN(SO2CF3)2 (LiTFSI), LiN(SO2C2F5)2 (LiBETI)LiClO4, lithium bis(oxalate)borate, lithium difluoro(oxalate)borate, LiSO3CF3, lithium 2-pentafluoroethoxy-1,1,2,2-tetrafluoroethanesulfonate and lithium 2-pentafluoroethoxy-1,1,2,2-tetrafluoroethanesulfonate (LiSO3C2F4OC2F5), and combinations thereof.

45. The process according to any one of claims 25 to 44, wherein the mixture in step c) is kneaded.

46. ​​The process according to claim 45, wherein the kneading torque (M / Nm) is between 1 and 20, and between 4 and 15.

47. The process of claim 46, wherein the kneading time is between 0 and 48 hours, optionally about 24 hours or less, 12 hours or less, optionally between 1 minute and 2 hours.

48. The process according to any one of the preceding claims, wherein in a further step, the mixed solid electrolyte (HSE) is further calendered, and / or coated on a surface, and / or passed through an extruder.

49. A mixed solid electrolyte (HSE) comprising: -Thiophosphate or oxide filler particles (FP), - Polymers including polyethylene oxide (PEO) and polyethylene glycol (PEG), - and lithium-ion conductive salts.

50. The HSE according to claim 49, wherein the filler particles (FP) are thiophosphate and / or oxide filler particles.

51. The HSE according to claim 49 or claim 50, wherein the particles are made of materials having the general formula Li x MeO y The material composition is given by y = (x + n) / 2, where 0 ≤ x ≤ 3, and Me is selected from metals with a valence of n, P or B, where n is 3, 4 or 5.

52. The HSE according to any one of claims 49 to 51, wherein the particles are composed of a material having a garnet-like crystal phase, the material having the empirical formula: Li 7+x-y M x II M 3-x III M 2-y IV M y V O 12 M II It is a divalent cation, M III It is a trivalent cation, M IV It is a tetravalent cation, M V It is a pentavalent cation, and 0≤x<3 and 0≤y<2, or a compound derived therefrom.

53. The HSE according to any one of claims 49 to 52, wherein the particles are composed of a material having a crystalline phase isomorphic to NaSICon, said material having the empirical formula: Li 1+x-y M 5+y M 3+x M 4+2-x-y (PO4)3, where x and y are in the range from 0 to 1, and (1+xy)>1, and M is a cation with a valence of +3, +4 or +5, or a compound derived therefrom.

54. The HSE according to any one of claims 49 to 53, wherein the filler particles are selected from the group consisting of lithium lanthanum tantalum zirconate (LLZTO), lithium lanthanum zirconate (LLZO), lithium lanthanum titanate oxide (LLTO), lithium superionic phosphorus sulfide (LSPS), lithium garnet phosphorus sulfide (LGPS), lithium phosphorus sulfide (LPS), lithium phosphorus sulfide (LPSCl), lithium aluminum titanium phosphate (LATP), lithium garnet solids (LGS), and / or mixtures thereof.

55. The HSE according to any one of claims 49 to 54, wherein the filler particles are uniformly distributed in the polymer.

56. The HSE according to any one of claims 49 to 55, wherein the average diameter x of the filler particles 50 For 5 μm or smaller, 3 μm or smaller, or 1 μm or smaller.

57. The HSE according to any one of claims 49 to 56, wherein the final content of the filler particles (FP) in the mixed solid electrolyte (HSE) is between >0 vol.-% and 15 vol.-%, optionally about 10 vol.-%.

58. The HSE according to any one of claims 49 to 57, wherein the filler particles in the HSE have a particle size of > 0.5 - 5 μm. 2 / cm 3 The total surface area.

59. The HSE according to any one of claims 49 to 58, wherein the filler particles are silanized and / or ground.

60. The HSE according to any one of claims 49 to 59, wherein the PEO:PEG ratio of PEO to PEG in the HSE is between 3:1 wt.-% and 5:1 wt.-%, and optionally the PEO:PEG ratio is about 4:1 wt.-%.

61. The HSE according to any one of claims 49 to 60, wherein the lithium-ion conductive salt in step e) is selected from LiAsF6, LiClO4, LiSbF6, LiPtCl6, LiAlCl4, LiGaCl4, LiSCN, LiAlO4, LiCF3CF2SO3, Li(CF3)SO3 (LiTf), LiC(SO2CF3)3, LiPF6, LiPF3(CF3)3 (LiFAP), LiPF4(C2O4) (LiTFOB), LiBF4, LiB(C2O4)2 (LiBOB), LiBF2(C2O4) (LiDFOB), LiB(C2O4)(C3O4)(LiMOB), Li(C2F5BF3) (LiFAB), Li2B 12 F 12 The group consisting of (LiDFB), LiN(FSO2)2 (LiFSI), LiN(SO2CF3)2 (LiTFSI), LiN(SO2C2F5)2 (LiBETI)LiClO4, lithium bis(oxalate)borate, lithium difluoro(oxalate)borate, LiSO3CF3, lithium 2-pentafluoroethoxy-1,1,2,2-tetrafluoroethanesulfonate and lithium 2-pentafluoroethoxy-1,1,2,2-tetrafluoroethanesulfonate (LiSO3C2F4OC2F5), and combinations thereof.

62. The HSE according to any one of claims 49 to 61, wherein the lithium conductive salt is uniformly distributed in the polymer.

63. The HSE according to any one of claims 49 to 62, wherein no H2S formation is detected within 48 hours after the production of the HSE.

64. The HSE according to any one of claims 49 to 63, wherein the interface resistance (at 20°C) of the HSE to the lithium metal anode is 100 Ω or less, 75 Ω or less, or 60 Ω or less.

65. The HSE according to any one of claims 49 to 64, wherein the polarization voltage (at 80°C) of the HSE is 50 mV or less, 40 mV or less, 5 mV or less, or 3 mV or less.

66. The HSE according to any one of claims 49 to 65, wherein the porosity (ε / %) of the HSE is 10.00 or less, 9.53 or less, 8.24 or less, 2.34 or less, 0.62 or less, or 0.35 or less.

67. The HSE according to any one of claims 49 to 66, wherein the porosity (ε / %) of the HSE is 10.00 or less.

68. The HSE according to any one of claims 49 to 67, wherein the HSE has an ionic conductivity of 1.4 × 10⁻⁶ at room temperature (RT). -5 S cm -1 With 6.2*10 -5 S cm -1 between.

69. The HSE according to any one of claims 49 to 68, wherein the number of transitions of the HSE is 0.12 or greater, 0.52 or greater, 0.55 or greater, 0.57 or greater, or 0.6 or greater.

70. The HSE according to any one of claims 49 to 69, wherein the filler particles in the HSE exhibit a crystallite size of 20 nm or greater, optionally 35 nm or greater, or 50 nm or greater.

71. An HSE produced by the process according to any one of claims 1 to 48.

72. A solid electrolyte membrane comprising the solid electrolyte material according to any one of claims 49 to 71.

73. Use of the solid electrolyte material according to any one of claims 49 to 72 in a solid-state battery, wherein the solid-state battery is optionally an all-solid-state lithium-ion battery.

74. Use of the solid electrolyte material according to claim 73 at temperatures between -60°C and +100°C, optionally between -40°C and +80°C.

75. Use of the solid electrolyte material according to any one of claims 73 or 74 in electric vehicles, portable electronic devices, energy storage, space exploration, medical technology (e.g., pacemakers), industrial applications (e.g., backup power supplies and high-performance equipment), aerospace (e.g., energy storage solutions for aircraft, satellites and spacecraft), distributed energy systems and / or emergency and rescue technologies.

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