Sodium ion conductor, method for the production thereof, and use of same

Abstract

The invention relates to a sodium ion conductor, in particular for use in a sodium-ion battery or solid-state sodium battery having more than 28 mol.% Na2O and at least one crystal phase, for which the ratio of all at least divalent ions having an ion radius of less than 69 pm (nr<69) to at least divalent ions having a radius of 69 pm (nr>69), nr<69 / nr≥69 is between 3 and 6. A sodium conductivity at room temperature of more than 10-5 S / cm can be achieved. The invention further relates to a method for producing such a sodium ion conductor and to the uses thereof, in particular as a component of a sodium ion battery or a solid-state sodium battery.

Description

[0001] Sodium-ion conductor, method for its production and its use. The present invention relates to a sodium-ion conductor, a method for its production, and the use of the sodium-ion conductor in a sodium-ion battery, in particular a sodium solid-state battery. Batteries are used in a wide variety of applications. They are indispensable in small portable electronic devices such as smartphones, tablets, or laptops, as well as on a larger scale, such as in electric cars or stationary energy storage systems. Lithium-ion batteries are frequently used, especially in applications requiring high energy density. The supply of lithium and other raw materials necessary for the production of these batteries, such as copper, cobalt, or manganese, is complex and sometimes associated with environmental problems. Sodium-ion batteries are being discussed as a rational alternative.These batteries are based on environmentally friendly raw materials with high global availability. They can be manufactured with either a liquid or a solid electrolyte. Organic liquid electrolytes generally have the disadvantage of being flammable and often toxic or environmentally harmful. Sodium batteries with water-based liquid electrolytes, which do not have this disadvantage, achieve only low energy densities and are therefore only conditionally suitable for mobile and stationary applications. Batteries with solid-state sodium ion conductors are proposed as a solution to these problems. Since these solid-state ion conductors often have insufficient conductivity at room temperature, they were used in the past in so-called thermal batteries at high temperatures (300°C or more). However, this solution is disadvantageous for both safety and cost reasons and is not suitable for mobile applications.Two classes of materials are known from the prior art that exhibit sufficiently high sodium conductivity even at room temperature: sodium β-aluminate and NaSICon (Na1+xZr2SixP3−xO12 and derivatives thereof). The production of these materials generally requires complex ceramic processes at high temperatures, as described, for example, in US 4049891 A and US 3475223 A, resulting in significant manufacturing costs. In particular, the production of pore-free components for batteries is difficult when using ceramic processes. Glass-based or glass-ceramic sodium ion conductors are also known, for example, from US 3829331 A or DE 2811688 A. Production via a melting process allows for large-scale manufacturing and, depending on the glass system, also shaping by rolling or drawing.However, the aforementioned systems with good conductivity, such as NaSICon or ^-Al₂O₃, are difficult to produce via glass melting due to their high melting temperatures. For example, US patent US 4465744 B for NaSICon describes that melting temperatures of 1600°C are necessary and the glass melt must be cooled very rapidly at 100°C / sec. In practice, these high melting temperatures lead to a lower yield due to the formation of melt remnants and uncontrolled devitrification, and also result in high energy consumption. Silicate sodium ion conductors with rare earth elements are described in US 4097345 A and US 4223077 A. They were produced via a solid-state reaction. The achieved conductivities reached a maximum of 0.1 S / cm at 200°C. However, sufficient ionic conductivities were only achieved at 200°C, not at room temperature.Production using a solvent-based process and spray drying has also been described, see EP0151925 A2. Here too, acceptable conductivities were only achieved at 300 °C. US application 2022271330 A describes a glass-ceramic ionic conductor with the composition Na. x M x Si x 0 x (M=Gd or Y, x integer), which has a high conductivity of >10 -4The sodium ion conductor exhibits high conductivity at room temperature (S / cm). However, its production requires a complex process involving various mixing and / or milling steps in organic solvents followed by a sintering step at temperatures exceeding 1000°C. The object of the present invention is therefore to provide a sodium ion conductor that exhibits high conductivity at room temperature and allows for efficient large-scale production. This object is achieved by the subject matter of the independent claims. Specific and preferred embodiments are described in the dependent claims and in the description of this disclosure.The invention relates to a sodium ion conductor suitable for use in a sodium ion or sodium solid-state battery, containing more than 28 mol% Na2O, and at least one crystalline phase for which the ratio of all at least divalent ions contained therein has an ionic radius of less than 69 pm (n. r<69 ) to at least divalent ions with a radius of at least 69 pm (nr>69), calculated as nr<69 / nr≥69, lies between 3 and 6. Or in other words, 3 < nr<69 / nr≥69 < 6. In an advantageous embodiment, this ratio in the crystal phase is 3 < nr<69 / nr≥69 < 5. Table 1 shows typical ionic radii of some cations: Si 4+ 54 pm P 5+ 52 pm S 6+ 43 pm B 3+ 41 pm Al 3+ 67.5 pm Fe 3+ 69 pm Ti 4+ 74.5 pm Zr 4+ 86 pm Mg 2+ 86 pm Y 3+ 104 pm Gd 3+ 108 pm Ca 2+ 114 pm La 3+117 pm The inventors recognized that such sodium ion conductors exhibit high sodium conductivity. High conductivity, as defined by the invention, is a sodium conductivity at room temperature of more than 10 -5 S / cm, advantageously more than 10 -4 S / cm is understood. Upper limits of 0.5 S / cm or 1 S / cm can be expected. The crystal phase of the sodium ion conductors advantageously has a mean cation charge k of 2 < k < 3, according to an advantageous embodiment a mean cation charge of 2.2 ≤ k ≤ 2.8; particularly advantageously 2.3 < k ≤ 2.6. The mean cation charge is calculated using the following formula: where n i represents the frequency of a cation i and k i whose charge. Table 2 shows examples for the calculation of nr<69 / nr>69 and k for different crystal phases: Crystal phase nr<69 / nr≥69 k Na3Zr2Si2PO12 (NaSICon) 1.5 3 Na3YSi3O93 2.57 Na9SmSi6O 166 2.25 Na5GdSi4O12 4 2.4 The sodium ion conductor, as described above, has at least one crystalline phase which advantageously comprises at least 70% (based on the total volume) of the sodium ion conductor and which has the aforementioned properties. This means that the sodium ion conductor may have further crystalline phases. Since it can be produced particularly efficiently via the melting route, as described herein, it may also contain a residual glass phase. According to a particularly advantageous embodiment, the aforementioned crystalline phase, the minimum proportion of which in the sodium ion conductor, as described, is at least 70 vol% and which is also referred to herein as the main crystalline phase, consists of at least 55%, preferably more than 60%, based on the volume, of the aforementioned sodium-conducting crystalline phase, which, as described, in particular has a ratio of 3 <n r<69 / n r≥69< 6. This naturally includes the fact that the main crystal phase consists at least substantially entirely of the aforementioned sodium-conducting crystal phase. In an advantageous embodiment, the crystal phase and / or main crystal phase is described by the following formula: Na 5+q (R)(M)4O 12±δ.R represents divalent, trivalent, tetravalent, or pentavalent ions, M represents Si and optionally P and / or B. q denotes the sodium excess compared to the stoichiometric composition, and preferably q ≥ 0. Trivalent ions selected from the rare earth elements, aluminum, and / or iron are particularly advantageous. Tetravalent ions are preferably selected from Zr, Hf, and / or Ti. Divalent ions selected from Mg, Ca, Sr, Ba, and / or Zn are equally advantageous. Pentavalent ions selected from tantalum and / or niobium are particularly advantageous. This includes the aforementioned components individually or in any combination. All elements are present in a fully oxidized state. Due to the different charges of the cations R and M, the O content may deviate by δ from the ideal composition.According to a preferred embodiment, the molar composition of the sodium ion conductor is given by (in mol%): Na₂O 28–60%, preferably 30–50%; RE₂O₃₀ - 15%, preferably 0.1–10%, particularly preferably 2–8%; SiO₂ 35–75%, preferably 40–60%; P₂O₅ 0–10%, preferably 0.1–8%, particularly preferably 0.5–5%; Al₂O₃₀ - 10%, preferably 0–5%; MgO + CaO + SrO + BaO; ZnO 0–10%, preferably 0–5%; B₂O₃₀ - 5%, preferably 0–3%, particularly preferably 0–1%; ZrO₂ + HfO₂ 0–<20%, preferably <15%; TiO₂ 0–<20%, preferably <15%, particularly preferably <5%; Fe₂O₃₀ - 15%, preferably 0-10%, particularly preferably 0-5% Nb2O5 + Ta2O5 0-10%, preferably 0-5%, SO30-10%, preferably 0-5%, particularly preferably <5% F+Cl+Br+I 0-10%, preferably 0-5%, particularly preferably <5% In a particularly preferred embodiment, the sodium ion conductor is free of Nb2O5 and / or Ta2O5.RE2O3 represents the sum of the rare earth oxides Sc2O3, Y2O3, La2O3, Ce2O3, Pr2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, and Lu2O3, including any combinations thereof. F, Cl, Br, and / or I may be present within the specified limits, either individually or in combination. The same principle applies to the use of the symbol '+', which indicates that the associated elements may be present individually or in combination. Preferably, RE2O3 is selected from Y2O3, Gd2O3, Nd2O3, Pr2O3, La2O3, and Yb2O3, each individually or in any combination. It should be emphasized that the preferred regions of one component can be combined with any regions of the other components. Or in other words, all the areas for components and / or component groups contained in this description can be combined with the areas for other components and / or component groups.The same applies to the selection of specific components. A particularly advantageous sodium ion conductor is a glass-ceramic ion conductor comprising at least one crystalline phase, especially the aforementioned main crystalline phase, and at least one residual glass phase, wherein the residual glass phase has a lower melting temperature than the crystalline phase. This means that the overall composition of the sodium ion conductor can differ from the composition of the crystalline phase. In an advantageous embodiment, the sodium ion conductor consists of a glass-ceramic with a main crystalline phase having a ratio of 3 < n. r<69 / n r≥69The product has a melting point of <6 or <5 and a residual glass phase that has a lower melting temperature than the crystal phase. The presence of the residual glass phase also has the advantage of positively influencing the sintering behavior. In one embodiment, the sum of the components Al₂O₃ + B₂O₃ + P₂O₅ is greater than 0.1 mol%, particularly preferably > 1 mol%. Upper limits of <30 mol%, <20 mol%, or <10 mol% can be specified. This improves glass formation during melt production. In a particularly preferred embodiment, the ratios of the cations in the sodium ion conductor are such that (P-Al) ∙ 0.2 + 1 < Na / R < (P-Al) ∙ 0.2 + 8, preferably (P-Al) ∙ 0.2 + 4 < Na / R < (P-Al) ∙ 0.2 + 7. R here stands for the metal cations R (RE, Al, Fe, Zr, Ti, Hf, Nb, Ta, Zn, Mg, Ca, Sr, Ba), RE stands for the rare earth cations. These and / or their selection have been described previously.In compositions that satisfy this condition, a particularly high proportion of the highly conductive Na⁵+q(R)(M)₄O₁₂±δ crystalline phase is formed during ceramicization. With a lower Na / R ratio, phases with a lower sodium content are preferred, while with a higher ratio, those with a higher sodium content are preferred. However, these crystalline phases generally exhibit lower conductivity, resulting in a lower overall conductivity of the sodium ionic conductor. It has also proven particularly advantageous if the sodium ionic conductor has a ratio of Na to the sum of all metal cations R that lies between 1 and 7, preferably between 2.4 and 6.8. Here, R represents Al, Fe, Zr, Ti, Hf, Nb, Ta, Zn, Mg, Ca, Sr, Ba, and / or combinations thereof. The ratio of all divalent and higher-valent metal cations R (RE, Al, Fe, Zr, Ti, Hf, Nb, Ta, Zn, Mg, Ca, Sr, Ba) and nonmetal cations M (Si, P, B), i.e.The R / M ratio is preferably in the range between 0.1 and 0.4, and particularly advantageous is the range between 0.2 and 0.3, or in other words, 0.2 < R / M < 0.3. This achieves an optimum with respect to meltability, glass formation, and the formation of highly conductive crystal phases. Preferably, the composition of the sodium ion conductors according to the invention satisfies the condition Na / (Si+P-RE-Fe-Al) < 2. It has been found that this reduces the formation of sodium-rich side phases such as the N9 phase. In this formula, '+' and '-' denote the mathematical operators, i.e., addition and subtraction. The P / Si ratio should be less than 1, preferably less than 0.5, and particularly preferably less than 0.2, since excessively high phosphorus contents lead to increased formation of side phases.According to a particularly advantageous embodiment, the sodium ion conductor is essentially free of toxic or environmentally harmful components such as Sb, As, Te, V, Pb, and Cd. "Essentially free" means that it contains at most impurities that are unavoidable in standard and economical production processes (e.g., due to raw materials). This means that the sodium ion conductor is specifically free of these elements. According to one embodiment, the sodium ion conductor contains polyvalent ions, preferably iron or titanium, and, in addition to its sodium ion conductivity, exhibits electronic conductivity, wherein the ratio of electronic to ionic conductivity is greater than 10. -4 , advantageously larger than 10 -3This material can be advantageously used as a cathode material or as an ion-conducting additive to an electrode material in a sodium-ion or sodium solid-state battery. According to a further embodiment, the sodium-ion conductor is essentially free of polyvalent ions, in particular free of Ce, Fe, V, Ti, Nb, and Mo. This embodiment can be advantageously used as an electrolyte or separator material, since polyvalent ions can reduce the stability of the material relative to other components in a battery or can result in electronic conductivity that leads to self-discharge of the battery when used as an electrolyte. According to a further embodiment, the sodium-ion conductor is essentially free of Ga, Ge, Ta, and W, since the use of these components can lead to environmental pollution or inefficient procurement processes.The term "essentially free" means that only impurities unavoidable in standard and economical production processes (e.g., due to raw materials) are present. According to one embodiment, the oxygen in the sodium ion conductor can be replaced by other anions to achieve improved conductivity. These anions can be halides or sulfate ions. However, the halide content should be limited to avoid impairing stability in the presence of atmospheric conditions and / or humidity; it is therefore below 10 mol%, preferably below 5 mol%, and particularly preferably below 2 mol%. The halides are selected from the group consisting of fluorine (F), chlorine (Cl), iodine (I), and brion (Br). According to one embodiment, the sodium ion conductor according to the invention is a glass ceramic.A glass-ceramic within the meaning of the present invention is understood to be a material that is produced by melting technology and subsequently transformed into a glass-ceramic by targeted cooling and / or subsequent heat treatment ("ceramization"). The material obtained after cooling the melt preferably contains less than 30% crystalline phase and is particularly preferably amorphous. During ceramization, the degree of ceramization, and thus the ratio of amorphous phase to crystalline phase, the microstructure, and optionally the type of crystalline phase, can be controlled by a suitable selection of the time and temperature conditions. The production of the sodium ion conductor according to the invention preferably takes place in the following steps: 1. Preparation and mixing of the raw materials 2. Melting of the raw materials at 1200-1650°C, preferably at 1300-1600°C 3. Casting and cooling of the glass melt, in particular as a casting or ribbons 4. Ceramization 5.Cold post-processing of the glass ceramic or grinding to produce sodium ion-conducting powder: Grinding the glassy material followed by ceramicization is possible, but not preferred, as partial sintering of the powder can occur during ceramicization. Furthermore, it has been observed that ceramicization of castings or ribbons, in contrast to ceramicization of powder, reduces the formation of side phases. The sodium ion conductor according to the invention can preferably be used as a component of a sodium-ion battery or a sodium solid-state battery. This includes the fact that the sodium ion conductor according to the invention can be used as a solid-state electrolyte, an additive to a liquid or polymer electrolyte, or as a separator in combination with liquid electrolytes. Solid-state electrolytes can also be used in high-temperature batteries (250°C – 350°C), for example, sodium-sulfur batteries or Na-NiCl batteries.Sodium-MeCl₂ batteries (Me = Na, Fe, Zn, and others) are possible as Ni-free alternatives. A membrane made from the sodium ion conductor according to the invention can also be used as an ion-selective membrane for chemical processes, e.g., for chemical syntheses using electrolysis or for recycling. Its use in sensors, e.g., gas sensors, is also possible. In a preferred embodiment, particularly as a further processed product, the sodium ion conductor is in powder form, advantageously with a particle size distribution of d₅₀ < 100 µm, preferably < 10 µm, and most preferably ≤ 3 µm. The sodium ion conductor or the powder described above can be used, in particular, for the production of a sodium-ion battery or a sodium solid-state battery.This ion-conducting powder is particularly advantageous for use in the production of thin membranes as an electrolyte or separator, or as a composite with electrode material to increase the ionic conductivity of the electrodes. This can be achieved by using binders, polymers, ionic liquids, and / or by means of a hot sintering process. The production of sintered bodies with other geometries (e.g., tubular shapes) is also possible. When a sintering process is used, the sintering temperature of the sodium ion conductor according to the invention is preferably below 1050°C, and particularly preferably below 1000°C. The sintering temperature according to the present invention is understood to be the temperature at which the sodium ion-conducting powder can be sintered into sintered bodies with a density of more than 90%, preferably more than 95%, of the theoretical density.The use of the ion-conducting powder as a starting material for a coating process to produce conductive coatings is also possible. The material according to the invention is suitable for the large-scale production of sodium ion conductors: common raw materials such as oxides, carbonates, hydroxides, or complex raw materials such as phosphates can be used. For melt-based production, costly grinding of the raw materials or the use of expensive nanoscale raw materials can be avoided. In production via a hot process (melting or sintering), low-melting-point components can be lost through evaporation or dust formation. This loss is usually compensated for by a superstoichiometric input weight. Melt-based production is advantageous here because the surface area to volume ratio of the produced material is more favorable (i.e.,The process time is lower than with a powder-based ceramic manufacturing process. If the sodium ion conductor is to be used further as a powder, it is advantageous in glass-ceramic manufacturing to first produce and ceramicize thin glass ribbons. Rapid cooling of these ribbons induces stresses within them, which reduce the process time during subsequent milling. Milling is preferably carried out by a dry milling process or by water milling followed by drying. The sodium ion conductor, especially in powder form, can be hygroscopic, which can lead to the formation of poorly conductive hydroxides or carbonates on the surface. Therefore, the ion-conducting powder is advantageously processed and stored in a dry atmosphere or under protective glass, or dried in a post-processing step after contact with (atmospheric) moisture.The invention is explained in more detail below using examples. Examples of compositions of sodium ion conductor materials according to the invention can be found in Table 3 (all values ​​in mol%). Examples 1-21 represent sodium ion conductors according to the invention, while Examples V1 to V6 in Table 4 are comparative examples. The abbreviation RE2O3 stands for the sum of the rare earth oxides: Sc2O3, Y2O3, La2O3, Ce2O3, Pr2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, and Lu2O3. Preferably, RE2O3 is selected from Y2O3, Gd2O3, Nd2O3, Pr2O3, La2O3, and Yb2O3, or combinations thereof. The materials listed in Table 1 were melted and homogenized using raw materials commonly used in the glass industry at temperatures of approximately 1350 °C to 1650 °C. Castings were made from the molten material and then annealed in a cooling furnace at the temperatures specified in the table, allowing the material to cool to room temperature.The castings were used to prepare test samples for ceramization. Alternatively, the molten glass was poured between two rotating rollers to produce ribbons, which were then ceramized. One- or two-stage programs were used for the ceramization, as specified in Tables 3 and 4. In two-stage programs, the starting glasses are first heated from room temperature to a nucleation temperature above Tg and held there for a sufficient time to allow nucleation. The samples are then heated to the ceramization temperature and held there as well. In one-stage programs, the samples are heated directly to the crystallization temperature and held there. Holding times for (optional) nucleation range from 0 minutes to 24 hours, advantageously up to 6 hours, followed by a ceramization step with a holding time of 5 minutes to 48 hours, advantageously 30 minutes to 12 hours.Holding times can still be replaced by slow heating rates. The crystal phases of the ceramicized samples were determined using XRD. The crystal phases listed in Tables 3 and 4 were determined by X-ray diffraction measurements on a Panalytical X'Pert Pro diffractometer (Almelo, Netherlands). CuK radiation (λ = 1.5060 Å) generated via a Ni filter was used as the X-ray source. Standard X-ray diffraction measurements on both powder and solid samples were performed under a Bragg-Brentano geometry (λ-2λ). The X-ray diffraction patterns were measured between 10° and 100° (2λ angles). The measurements were performed on ground sample material. A distinction was made between the main crystal phase and the secondary crystal phase, with the main crystal phase being defined as the crystal phase with the largest proportion relative to all crystal phases.In all examples, the main crystal phase has a crystal structure of the form Na⁵ + q(R)(M)⁴O₁₂±δ. In examples 10-13, 19-21, and the comparative example V5, the proportion of the main crystal phase, as well as all crystal phases present in the glass ceramic, was additionally determined using Riedveld analysis. For the calculation of the average cation charge, it was assumed that the composition of the crystal phase essentially corresponds to the molar proportions of the composition, since the minor phases are present only in small amounts in most cases. The abbreviation "nb" stands for "not determined." The conductivity at room temperature (RT) was also determined for samples from examples 10-14. For this purpose, the sample is sputtered on both sides with a gold layer and measured at room temperature using electrochemical impedance spectroscopy (EIS).The stated total conductivity is composed of the conductivity of the ion-conducting crystallites ("grain conductivity") and a grain boundary contribution, which exhibits a lower conductivity. The grain boundary contribution includes both the (lower) conductivity of an amorphous phase and, in the case of sintered bodies, pores. Unless explicitly stated otherwise, in the context of this invention, conductivity or room-temperature conductivity refers to the total conductivity at room temperature. Ribbons were also produced from the composition in Example 14 by pouring the molten glass onto two counter-rotating metal rollers. The ribbons were ceramicized according to the temperature program specified in Table 1 and then ground into a powder with a particle size of d50 approximately 1 µm. From this powder, pellets were produced and sintered at 900°C–1000°C. The conductivity of the pellets was in the range of 10 for all samples.-3 S / cm, the density >90% of the theoretical density. The comparative examples V1 and V2 show typical NaSICon compositions. Composition V1 could be melted at temperatures of approximately 1650°C, but immediately after casting already showed numerous side phases and consequently very low conductivity. Composition V2 was not fusible. In both examples, the ion ratio n r<69 / n r≥69<3. In contrast, comparison example 3 shows a composition where the ratio nr<69 / nr≥69 > 9. The resulting main crystal phase exhibits no or only low sodium conductivity. In comparison example V4, the average cation charge k is too high; here too, the desired ion-conducting crystal phase does not form during ceramicization. Examples V5 and V6 demonstrate the significance of the relation (P-Al) ∙ 0.2+4 < Na / R < (P-Al) ∙ 0.2+7. Example V5 does satisfy the condition (P-Al) ∙ 0.2+1. <Na / R<(P-Al) ∙ 0,2+8, jedoch ist die Bedingung (P-Al) ∙ 0,2 +4 < Na / R nicht erfüllt. Bei der Keramisierung zeigt sich die Tendenz solcher Zusammensetzungen statt der erfindungsgemäßen Kristallphase Na 5+q (R)(M)4O 12±δto form the less conductive phase Na3YSi3O9. Example V6 forms the crystal phase Na9(Y, Gd)Si5O18 as the main crystal phase. Here, the condition Na / R<(P-Al)+7 is not fulfilled. Compositions like those in examples V5 and V6, which do fulfill the condition (P-Al) ∙ 0.2+1 <Na / R<(P-Al)+8 erfüllen, nicht jedoch zu dem bevorzugten Bereich gehören, in dem auch die Bedingung (P-Al) ∙ 0,2+4 < Na / R < (P-Al) ∙ 0,2+7 erfüllt ist, können in der Regel durch eine angepasste Keramisierung in einen erfindungsgemäßen Ionenleiter überführt werden, wozu allerdings in der Regel eine aufwändige Prozessoptimierung notwendig ist.

[0002] Example 1 2 3 Al2O30 0.98 0 B2O30 0 0 Fe2O30 0 0 Gd2O30 5.88 5.88 Na2O 35.71 39.22 38.24 P2O5 0 2.94 2.94 SiO2 57.14 50.98 52.94 Y2O3 7.14 0 0 Na / R 5.00 5.71 6.50 R / M 0.25 0.24 0.20 P / Si 0.00 0.12 0.11 P-Al 0.00 2.63 4.00 (P-Al)∙ 0.2+1 < Na / R<(P-Al) 0.2+8 yes yes yes (P-Al) 0.2+4 < Na / R<(P-Al) 0.2+7 yes yes yes Na / (Si+P-RE-Fe-Al) 1.67 1.82 1.63 Melting temperature (°C)1350 1350 1350K eimbildungstemp.(°C) 640 - - K eimbildungszeit (h) 6 - - Crystallization temperature (°C) 1000 950 950 Crystallization time (h) 6 12 12 Main crystal phase Na5YSi4O12 Na4Gd0,6Al0,1P0,3Si2,6O9 Na3,9Gd0,6P0,3Si2,7O9 Secondary phase Na9YSi6O18 Na9GdSi6O18 Na9GdSi6O18 nr<69 / nr≥69 4.0 5.0 5.0 k 2.4 2.37 2.4 Conductivity at RT (S / cm) nbnbnb Table 3: Examples of implementation

[0003] Example 4 5 6 Al2O3 0 0 0 B2O3 0 0 1.43 Fe2O3 7.14 7.25 7.14 Gd2O3 0 0 0 Na2O 35.71 35.51 37.14 P2O50 0.72 0 SiO25 7.14 56.52 54.29 Y2O30 0 0 Na / R 5.00 4.90 5.20 R / M 0.25 0.25 0.25 P / Si 0.00 0.03 0.00 P-Al 0.00 1.01 0.00 (P-Al) 0.2+1 < Na / R<(P-Al) 0.2+8 yes yes yes (P-Al) 0.2+4 < Na / R<(P-Al) 0.2+7 yes yes yes Na / (Si+P-RE-Fe-Al) 1.67 1.63 1.86 Melting point (°C) 1350 1350 1350K eimbildungstemp.(°C) 466 450 420K eimbildungszeit (h) 6 6 6 Crystallization temperature (°C) 800 772 690 Crystallization time (h) 6 6 6 Main crystal phase Na5FeSi4O 12 N / a 4,9 FeP 0,1 Si 3,9 O 12 N / a 5,2 FeB 0,2 Si 3,8 O 12 Na2(Si,Fe)O3+ Side phase Na2SiO3 + Traces Na2SiO3 + Traces Traces nr<69 / nr≥69 4.0 4.0 4.0 k 2.4 2.42 2.38 Conductivity at RT (S / cm) nbnbnb Table 3: Examples of implementation (continued)

[0004] Example 7 8 9 Al2O30 0 0 B2O30 3.57 0 Fe2O3 3.57 7.14 0 Gd2O3 0 0 0 Na2O 32.14 39.29 32.14 P2O5 0 0 0 SiO2 57.14 50.00 57.14 Y2O30 0 3.57 ZrO2 7.14 0 7.14 Na / R 4.50 5.50 4.50 R / M 0.25 0.25 0.25 P / Si 0.00 0.00 0.00 P-Al 0.00 0.00 0.00 (P-Al) 0.2+1 < Na / R<(P-Al) 0.2+8 yes yes yes (P-Al) 0.2+4 < Na / R<(P-Al) 0.2+7 no yes no Na / (Si+P-RE-Fe-Al) 1.29 2.20 1.29 Melting point (°C) 1350 1350 1350K eimbildungstemp.(°C) 480 410 - K eimbildungszeit (h) 6 6 - Crystallization temperature (°C) 800 640 950 Crystallization time (h) 6 6 12 Main crystal phase Na 4,5 Fe 0,5 Zr 0,5 Si4O 12 N / a 5,5 FeB 0,5 Si 3,5 O 12 N / a 4,5 Y 0,5 Zr 0,5 Si4O 12 Side phase ZrSiO4Na2(Si,Fe)O3+ traces unknown phase n r<69 / n r≥69 4.0 4.0 4.0 k 2.53 2.29 2.53 Conductivity at RT (S / cm) nbnbnb Table 3: Examples of implementation (continued)

[0005] Example 10 11 12 Al2O3 0.98 1.02 0.00 B2O30 0 0.98 Fe2O30 0 0 Gd2O30 6.12 5.88 Na2O 39.22 36.73 39.22 P2O5 2.94 3.06 2.94 SiO2 50.98 53.06 50.98 Y2O3 5.88 0 0 ZrO20 0 0 Na / R 5.71 5.14 6.67 R / M 0.24 0.24 0.20 P / Si 0.12 0.12 0.12 P-Al 2.63 2.78 3.95 (P-Al) 0.2+1 < Na / R<(P-Al) 0.2+8 yes yes yes (P-Al) 0.2+4 < Na / R<(P- Al) 0.2+7 yes yes yes Na / (Si+P-RE-Fe-Al) 1.82 1.64 1.74 Melting temperature (°C)1350 1350 1350K eimbildungstemp.(°C) - - - K eimbildungszeit (h) - - - Crystallization temperature (°C) 950 950 950 Crystallization time (h) 12 12 12 Main crystal phase Na4Y 0,6 Al 0,1 P 0,3 Si 2,6 O9Na 3,6 Gd 0,6 Al 0,1 P 0,3 Si 2,6 O9Na4Gd 0,6 B 0,1 P 0,3 Si 2,6 O9 Secondary phase AlPO4- - Proportion of main crystal phase 98% 100% 100% nr<69 / nr≥69 5.0 5.0 4.0 k 2.41 2.44 2.37 Conductivity at RT (S / cm) 2.22∙10 -3 5.73∙10 -3 1.26∙10 -3Table 3: Examples of Implementation (continued) Example 13 14 15 Al₂O 30.49 0.98 0 B₂O 30.49 0 0 Fe₂O 30 0 0 Gd₂O 35.88 5.88 0 Na₂O 39.22 39.22 30.36 P₂O₅ 2.94 2.94 0 SiO₂ 50.98 50.98 57.14 TiO₂ 0 0 3.57 Y₂O₃ 0 0 1.79 ZrO₂ 0 0 7.14 Na / R 6.15 5.71 4.25 R / M 0.22 0.24 0.25 P / Si 0.12 0.12 0.00 P-Al 3.29 2.63 0.00 (P-Al) 0.2+1 < Na / R<(P-Al) 0.2+8 yes yes yes (P-Al) 0.2+4 < Na / R<(P-Al) 0.2+7 yes yes no Na / (Si+P-RE-Fe-Al) 1.78 1.82 1.13 Melting temperature (°C) 1350 1350 1400 K eimbildungstemp.(°C) - - - K eimbildungszeit (h) - - - Crystallization temperature (°C) 950 950 950 Crystallization time (h) 12 12 12 Na4Gd0.6 Na4.25Y0.25 Main crystal phase B 0,05 Al 0,05 P 0,3 Si 2,6 O9Na4Gd 0,6 Al 0,1 P 0,3 Si 2,6 O9Ti 0.25 Zr 0.5 Si4O 12 Side phase - - Trace fraction of main crystal phase 100% nbnb nr<69 / nr≥69 5.0 5.0 4.0 k 2.37 2.37 2.59 Conductivity at RT (S / cm) 3.20∙10 -3 3.42∙10 -3Table 3: Examples of Implementation (continued) Example 16 17 18 Al₂O₃₀ 1.79 0 B₂O₃ 0 0 0 Fe₂O₃₀ 0 0 Gd₂O₃ 0 0 0 Na₂O 30.36 32.14 30.36 P₂O₅ 0 0 0 SiO₂ 57.14 57.14 57.14 TiO₂ 0 0 3.57 Y₂O₃ 1.79 1.79 1.79 ZrO₂ 10.71 7.14 7.14 Na / R 4.25 4.50 4.25 R / M 0.25 0.25 0.25 P / Si 0.00 0.00 0.00 P-Al 0.00 -2.63 0.00 (P-Al) 0.2+1 < Na / R<(P-Al) 0.2+8 yes yes yes (P-Al) 0.2+4 < Na / R<(P-Al) 0.2+7 no no no Na / (Si+P-RE-Fe-Al) 1.13 1.29 1.13 Melting temperature (°C)1600 1600 1600K eimbildungstemp.(°C) - - - K eimbildungszeit (h) - - - Crystallization temperature (°C) 800 800 950 Crystallization time (h) 12 12 12 Na4.25Y0.25 Main crystal phase Na 4,25 Y 0,25 Zr 0.75 Si4O 12 N / a 4,5 Y 0,25 Al 0,25 Zr 0,5 Si4O 12 Ti 0.25 Zr 0.5 Si4O 12 Side phase unknown. Phase unknown. Phase n r<69 / n r≥694.0 4.0 4.0 K 2.59 1.80 1.31 Conductivity at RT (S / cm) nb 0.25 0.25 Table 3: Examples of Implementation (continued) Example 19 20 21 Al2O3 1.00 0.99 0.98 Gd2O3 6.24 5.74 6.57 Na2O 38.51 39.51 37.86 P2O5 4.01 3.98 2.44 SiO2 50.23 49.78 52.16 Na / R 5.31 5.87 5.01 R / M 0.25 0.23 0.26 P / Si 0.16 0.16 0.09 P-Al 4.02 3.98 1.97 (P-Al) 0.2+1 < Na / R<(P- Al) 0.2+8 yes yes yes (P-Al) 0.2+4 < Na / R<(P- A l) 0,2+7 no yes yes Na / (Si+P-RE-Fe-Al) 1.76 1.79 1.81 Melting point (°C) 1600 1600 1600 Nucleation point (°C) - - - K eimbildungszeit (h) - - - Crystallization temperature (°C) 950 950 950 Crystallization time (h) 12 12 12 Na3.83Gd0.62 Na3.97Gd0.58 Na3.85Gd0.67 Main crystal phase Al 0,1 P 0.4 Si 2,5 O9Al 0,1 P 0.4 Si 2,5 O9Al 0,1 P 0,25 Si 2,65 O9 Secondary phase Traces Traces Proportion of main crystal phase 94% 96.9% 90.5% n r<69 / n r≥694.84 5.17 4.48 k 2.41 2.39 2.39 Conductivity at RT (S / cm) nbnbnb Table 3: Examples of Implementation (continued) Example 22 23 24 Al2O3 0.98 1.00 0.99 B2O3 0.00 0.00 0.00 CaO 0.00 0.00 0.00 Fe2O3 0.00 0.00 0.00 Gd2O3 6.57 6.25 5.75 La2O3 0.00 0.00 0.00 MgO 0.00 0.00 0.00 Na2O 37.86 38.50 39.51 P2O5 2.44 2.41 3.98 SiO2 52.16 50.23 49.77 TiO2 0.00 0.00 0.00 Y2O3 0.00 0.00 0.00 ZrO2 0.00 0.00 0.00 Na / R 5.01 5.31 5.86 R / M 0.26 0.26 0.23 P / Si 0.09 0.10 0.16 P-Al 1.97 1.93 3.97 (P-Al)*0.2+1 <Na / R<(P-Al)*0.2+8 ja ja ja (P-Al)*0.2+4<Na / R<(P-Al)*0.2+7 ja ja ja Na / (Si+P-RE-Fe-Al) 1.81 1.90 1.79 Schmelztemperatur (°C) 1500.00 1500.00 1500.00 Kühltemperatur (°C) 500.00 500.00 500.00 Keimbildungstemperatur (°C) - - - Keimbildungszeit (h) - - - Kristallisationstemperatur (°C) 950.00 950.00 950.00 Kristallisationszeit (h) 12.00 12.00 12.00 Hauptkristallphase Na5,13Gd0.89 Na5,11Gd0.83 Na5,29Gd0.77 Al 0,13 P 0,33 Si 3,53 O1Al 0,13 P 0,53 Si 3,33 O1Al0,13 P 0,53 And 3,33O12 2 2 Side phases Na9YSi6O18 Traces Traces nr<69 / nr>69 3.78 3.79 4.28 k 2.39 2.36 2.39 Conductivity at room temperature (S / cm) 1.90E-03 9.47E-04 1.87E-03 Table 3: Examples of implementation (continued) Example 25 26 27 Al2O3 0.98 0.37 0.36 B2O3 0.00 0.00 0.00 CaO 0.00 0.00 0.00 Fe2O3 0.00 0.00 0.00 Gd2O3 5.24 2.22 2.19 La2O3 0.00 1.11 0.73 MgO 0.00 0.00 1.46 Na2O 40.53 35.13 35.40 P2O5 3.94 2.22 2.19 SiO2 49.31 54.51 54.01 TiO2 0.00 0.00 0.00 Y2O3 0.00 2.22 2.19 ZrO2 0.00 2.22 1.46 Na / R 6.52 5.94 6.47 R / M 0.22 0.20 0.19 P / Si 0.16 0.08 0.08 P-Al 3.93 2.58 2.55 (P-Al)*0.2+1 <Na / R<(P-Al)*0.2+8 ja ja ja (P-Al)*0.2+4<Na / R<(P-Al)*0.2+7 ja ja ja Na / (Si+P-RE-Fe-Al) 1.81 1.42 1.45 Schmelztemperatur (°C) 1500.00 1350.00 1600.00 Kühltemperatur (°C) 500.00 500.00 500.00 Keimbildungstemperatur (°C) - - - Keimbildungszeit (h) - - - Kristallisationstemperatur (°C) 950.00 950.00 950.00 Kristallisationszeit (h) 12.00 12.00 12.00 Hauptkristallphase Na5,48Gd0.70 Na5,48Gd0.70 Na4.85Y0.3Gd0.3Zr0.1 Al0,13 Q 0,53 Si 3,33 Al 0,13 Q 0,53 Si 3,33 Day 0.1 Mg 0.1 Al 0.05 Q 0.3 Si 3.7O 12 12 12 Side phases Na9YSi6O18 AlPO4 AlPO4 nr<69 / nr>69 4.60 4.19 4.21 k 2.36 2.48 2.45 Conductivity at room temperature 2.13E-03 2.90E-04 8.00E-04 (S / cm) Table 3: Examples of implementation (continued) Example 28 29 30 Al2O3 0.95 0.98 0.00 B2O3 0.00 0.00 0.00 CaO 0.00 0.00 0.00 Fe2O3 0.00 0.00 0.00 Gd2O3 0.00 0.00 0.00 La2O3 0.00 0.00 0.00 MgO 0.00 0.00 0.00 Na2O 38.86 40.53 36.42 P2O5 2.41 3.94 1.46 SiO2 51.70 49.31 55.35 TiO2 0.00 0.00 0.00 Y2O3 6.07 5.24 6.77 ZrO2 0.00 0.00 0.00 Na / R 5.53 6.52 5.38 R / M 0.25 0.22 0.23 P / Si 0.09 0.16 0.05 P-Al 1.97 3.93 2.01 (P-Al)*0.2+1 <Na / R<(P-Al)*0.2+8 ja ja ja (P-Al)*0.2+4<Na / R<(P-Al)*0.2+7 ja ja ja Na / (Si+P-RE-Fe-Al) 1.83 1.81 1.63 Schmelztemperatur (°C) 1500.00 1500.00 1500.00 Kühltemperatur (°C) 500.00 500.00 500.00 Keimbildungstemperatur (°C) - - - Keimbildungszeit (h) - - - Kristallisationstemperatur (°C) 950.00 950.00 950.00 Kristallisationszeit (h) 12.00 12.00 12.00 Hauptkristallphase Na5.31Y0.83Al0.13 Na 5.48 Y 0.7 Al0.13 Na5Y0.93P 0.33 And 3.53 A 12 P 0.53 Si 3.33 O 12.0 P 0.2 And 3.8 A 12Side phases Na9YSi6O18 Na9YSi6O18 Na3YSi3O9 nr<69 / nr>69 4.03 4.60 4.30 k 2.37 2.36 2.42 Conductivity at room temperature (S / cm) 1.36E-03 1.19E-03 4.25E-04 Table 3: Examples of implementation (continued) Example 31 32 33 Al2O3 0.98 0.98 0.74 B2O3 0.00 0.00 0.00 CaO 0.00 0.00 0.00 Fe2O3 0.00 0.00 0.00 Gd2O3 0.00 0.00 0.00 La2O3 0.00 0.00 0.00 MgO 0.00 0.00 0.00 Na2O 41.04 37.86 37.50 P2O5 3.92 2.44 2.94 SiO2 49.09 52.16 51.47 TiO2 0.00 0.00 0.00 Y2O3 4.97 6.57 4.41 ZrO2 0.00 0.00 2.94 Na / R 6.90 5.01 5.67 R / M 0.21 0.26 0.23 P / Si0.6 0.16 0.09 0.11 P-Al 3.90 1.97 3.03 (P-Al)*0.2+1 <Na / R<(P-Al)*0.2+8 ja ja ja (P-Al)*0.2+4<Na / R<(P-Al)*0.2+7 ja ja ja Na / (Si+P-RE-Fe-Al) 1.82 1.81 1.59 Schmelztemperatur (°C) 1500.00 1500.00 1600.00 Kühltemperatur (°C) 500.00 500.00 500.00 Keimbildungstemperatur (°C) - - - Keimbildungszeit (h) - - - Kristallisationstemperatur (°C) 950.00 950.00 950.00 Kristallisationszeit (h) 12.00 12.00 12.00 Hauptkristallphase Na5.57Y0.67Al0.13 Na5.13Y0.89Al0.13 Na5.1Y0.6Zr0.2Al0.1 P. 0.53 Si 3.33 O 12 P 0.33 Si 3.53 O 12 P 0.4 Si 3.5 O 12 Side phases AlPO4AlPO4Na3PO4+unknown phase nr<69 / nr>69 4.79 3.78 4.33 k 2.34 2.39 2.42 Conductivity at room temperature 5.17E-04 3.57E-03 4.00E-04 (S / cm) Table 3: Examples of implementation (continued) Example 34 35 36 Al2O3 0.74 0.74 0.72 B2O3 0.00 0.00 0.00 CaO 0.00 0.00 0.00 Fe2O3 0.00 0.00 0.00 Gd2O3 0.00 0.00 0.00 La2O3 0.00 0.74 0.00 MgO 0.00 0.00 1.45 Na2O 36.03 37.50 37.68 P2O5 2.94 2.94 2.90 SiO2 51.47 51.47 50.72 TiO2 0.00 0.00 0.00 Y2O3 2.94 3.68 3.62 ZrO2 5.88 2.94 2.90 Na / R 5.44 6.38 6.50 R / M 0.23 0.21 0.21 P / Si 0.11 0.11 0.11 P-Al 3.09 3.03 3.00 (P- yes yes yes Al)*0.2+1 <Na / R<(P- Al)*0.2+8 (P- ja ja ja Al)*0.2+4<Na / R<(P- Al)*0.2+7 Na / (Si+P-RE-Fe-Al) 1.44 1.55 1.58 Schmelztemperatur 1600.00 1600.00 1600.00 (°C) Kühltemperatur (°C) 500.00 500.00 500.00 Keimbildungstemper - - - atur (°C) K eimbildungszeit (h) - - -Crystallization temperature 950.00 950.00 950.00 temperature (°C) Crystallization time (h) 12.00 12.00 12.00 Main crystal phase Na 4.9 Y 0.4 Zr 0.4 Al 0.1 P 0.4 N / a 5.1 Y 0.5 Zr 0.2 La 0.1 Al 0.1 P 0. N / a 5.2 Y 0.5 Zr 0.2 Mg 0.1 Al 0.1 P 0. Si3.5O12 4Si3.5O12 4Si3.5O12 Side phases Na3PO4+unknown Na3PO4+unknown Na3PO4+unknown Phase Phase Phase n r <69 / n r>69 4.33 4.33 4.33 k 2.47 2.42 2.40 Conductivity at room temperature (S / cm) 2.50E-05 5.30E-04 1.56E-04 Table 3: Examples of implementation (continued) Example 37 38 39 Al2O3 0.73 0.70 0.74 B2O3 0.00 0.00 0.00 CaO 0.00 0.00 0.00 Fe2O3 0.00 0.00 0.00 Gd2O3 0.00 0.00 0.00 La2O3 0.00 0.00 0.00 MgO 0.00 0.00 0.00 Na2O 32.85 33.33 35.71 P2O5 0.00 1.48 1.43 SiO2 56.93 54.81 52.86 TiO2 0.00 0.00 0.00 Y2O3 3.65 3.70 3.57 ZrO2 5.84 5.93 5.71 Na / R 4.50 4.52 4.98 R / M 0.26 0.26 0.26 P / Si 0.00 0.05 0.05 P-Al -1.06 1.12 0.97 (P-Al)*0.2+1 <Na / R<(P-Al)*0.2+8 ja ja ja (P-Al)*0.2+4<Na / R<(P-Al)*0.2+7 ja ja ja Na / (Si+P-RE-Fe-Al) 1.36 1.36 1.52 Schmelztemperatur (°C) 1600.00 1600.00 1600.00 Kühltemperatur (°C) 500.00 500.00 500.00 Keimbildungstemperatur (°C) - - - Keimbildungszeit (h) - - - Kristallisationstemperatur (°C) 950.00 950.00 950.00 Kristallisationszeit (h) 12.00 12.00 12.00 Hauptkristallphase Na 4.5 Y 0.5 Zr 0.4 N / a 4.5 Y 0.5 Zr 0.4 Na5Y 0.5 Zr0.4 TO l 0.1 Si 3.9 O 11.75 Al 0.1 P 0.2 Si 3.7 O 11.85 To the 0.1 P 0.2 Yeah 3.7 EITHER 12.1Side phases Na4Zr2Si3O12 Na9YSi6O18+ Na3YSi2O7 Na3YSi2O7 nr<69 / nr>69 3.90 3.92 3.89 k 2.50 2.52 2.44 Conductivity at room temperature 2.80E-05 7.80E-05 4.44E-05 (S / cm) Table 3: Examples of implementation (continued) Example 40 41 42 Al2O3 0.71 0.73 0.74 B2O3 0.00 0.00 0.00 CaO 0.00 0.00 0.00 Fe2O3 0.00 0.00 0.00 Gd2O3 0.00 0.00 0.00 La2O3 0.73 0.74 0.00 MgO 1.46 1.48 0.00 Na2O 32.85 33.33 35.56 P2O5 0.00 1.48 1.48 SiO2 56.93 54.81 55.56 TiO2 0.00 0.00 0.00 Y2O3 2.92 2.96 6.67 ZrO2 4.38 4.44 0.00 Na / R 5.64 5.64 4.80 R / M 0.20 0.20 0.25 P / Si 0.00 0.05 0.05 P-Al -1.04 1.08 1.03 (P-Al)*0.2+1 <Na / R<(P-Al)*0.2+8 ja ja ja (P-Al)*0.2+4<Na / R<(P-Al)*0.2+7 ja ja ja Na / (Si+P-RE-Fe-Al) 1.32 1.32 1.63 Schmelztemperatur (°C) 1600.00 1600.00 1500.00 Kühltemperatur (°C) 500.00 500.00 500.00 Keimbildungstemperatur (°C) - - - Keimbildungszeit (h) - - - Kristallisationstemperatur (°C) 950.00 950.00 950.00 Kristallisationszeit (h) 12.00 12.00 12.00 Hauptkristallphase Na 4.5 Y 0.4 Zr 0.3La 0.1 Na 4.72 Y 0.96 Na 4.8 Y 0.9 Al 0.1 Mg0.1Al0.1Si3.9O11.65 Al0.1Si4.01O12 P0.2Si3.75O11.9Nebenphasen Na3YSi3O9+Na3YSi2O Na3PO4 Na3YSi3O9 7 n r <69 / n r>69 3.91 3.91 3.95 k 2.48 2.50 2.44 Conductivity at room temperature 3.61E-05 4.42E-05 1.06E-04 (S / cm) Table 3: Examples of implementation (continued) Example 43 44 45 Al2O3 0.74 0.74 0.73 B2O3 0.00 0.00 0.00 CaO 0.00 0.00 1.46 Fe2O3 0.00 0.00 0.00 Gd2O3 0.00 0.00 0.00 La2O3 0.74 0.00 0.00 MgO 0.00 0.00 0.00 Na2O 35.56 34.81 35.04 P2O5 1.48 1.48 1.46 SiO2 55.56 55.56 54.74 TiO2 0.00 0.00 0.00 Y2O3 5.93 5.93 5.11 ZrO2 0.00 1.48 1.46 Na / R 5.33 4.70 5.33 R / M 0.23 0.25 0.23 P / Si 0.05 0.05 0.05 P-Al 1.03 1.04 1.03 (P-Al)*0.2+1 <Na / R<(P-Al)*0.2+8 ja ja ja (P-Al)*0.2+4<Na / R<(P-Al)*0.2+7 ja ja ja Na / (Si+P-RE-Fe-Al) 1.57 1.54 1.52 Schmelztemperatur (°C) 1500.00 1500.00 1500.00 Kühltemperatur (°C) 500.00 500.00 500.00 Keimbildungstemperatur (°C) - - - Keimbildungszeit (h) - - - Kristallisationstemperatur (°C) 950.00 950.00 950.00 Kristallisationszeit (h) 12.00 12.00 12.00 Hauptkristallphase Na 4.8 Y 0.8 La 0.1 N / a 4.7 Y 0.8 Zr 0.1 N / a 4.8 Y0.7 Zr 0.1 Al0.1P0.2Si3.75O11.9 Al0.1P0.2 Ca0.1Al0.1P0.2Si3.75O11. Si 3.75 O 11.9 9 Side phases Na3YSi3O9Na3YSi3O9Na3(Al)PO4n r <69 / n r>69 3.95 3.95 3.95 k 2.44 2.47 2.44 Conductivity at room temperature 3.49E-04 3.43E-04 6.72E-04 (S / cm) Table 3: Examples of implementation (continued) Example 46 47 48 Al2O3 0.73 0.73 0.72 B2O3 0.00 0.00 0.00 CaO 0.00 0.00 0.00 Fe2O3 0.00 0.00 0.00 Gd2O3 0.00 0.00 0.00 La2O3 0.00 0.73 0.72 MgO 1.46 1.46 1.44 Na2O 35.04 35.04 36.82 P2O5 1.46 1.46 2.53 SiO2 54.74 54.74 51.99 TiO2 0.00 0.00 0.00 Y2O3 5.11 4.38 4.33 ZrO2 1.46 1.46 1.44 Na / R 5.33 6.00 6.38 R / M 0.23 0.20 0.20 P / Si 0.05 0.05 0.10 P-Al 1.03 1.03 2.49 (P- yes yes yes Al)*0.2+1 <Na / R< (P-Al)*0.2+8 (P- ja ja ja Al)*0.2+4<Na / R< (P-Al)*0.2+7 Na / (Si+P-RE-Fe- 1.52 1.48 1.57 Al) Schmelztempera 1500.00 1500.00 1500.00 tur (°C) Kühltemperatur 500.00 500.00 500.00 (°C) Keimbildungstem - - - peratur (°C) Keimbildungszeit - - - (h) Kristallisationste 950.00 950.00 950.00 mperatur (°C) Kristallisationszei 12.00 12.00 12.00 t (h) Hauptkristallphas Na 4.8 Y 0.7 Zr 0.1 Mg 0.1 Al 0.1 P Na 4.8 Y0.6 Zr 0.1 Do 0.1 Mg 0.1 It 0.1 And 5.1 Y 0.6 Zr 0.1 Do 0.1 Mg 0.1 It 0.1 and 0.2 Si 3.75 O 11.9 P 0.2 Si 3.75 O 11.9 P 0.35 Si 3.6 O 12.12 Nebenphase Na3(Al)PO4Na3(Al)PO4Na3(Al)PO4n r <69 / n r>69 3.95 3.95 3.95 k 2.44 2.44 2.41 Conductivity at room temperature (S / cm) 1.24E-03 8.92E-04 3.22E-04 Table 3: Examples of implementation (continued) Example 49 50 51 Al2O3 0.72 0.74 0.74 B2O3 0.00 0.00 0.00 CaO 0.00 0.00 0.00 Fe2O3 0.00 0.00 0.00 Gd2O3 0.00 0.00 0.00 La2O3 0.72 0.00 0.00 MgO 1.45 0.00 0.00 Na2O 34.78 34.19 33.46 P2O5 0.00 0.00 0.00 SiO2 56.52 58.09 58.09 TiO2 0.00 0.00 0.00 Y2O3 4.35 6.99 6.25 ZrO2 1.45 0.00 1.47 Na / R 6.00 4.43 4.33 R / M 0.21 0.27 0.27 P / Si 0.00 0.00 0.00 P-Al -1.03 -1.04 -1.05 (P-Al)*0.2+1 <Na / R<(P-Al)*0.2+8 ja ja ja (P-Al)*0.2+4<Na / R<(P-Al)*0.2+7 ja ja ja Na / (Si+P-RE-Fe-Al) 1.50 1.60 1.52 Schmelztemperatur (°C) 1500.00 1500.00 1500.00 Kühltemperatur (°C) 500.00 580.00 580.00 Keimbildungstemperatur (°C) - - - Keimbildungszeit (h) - - - Kristallisationstemperatur (°C) 950.00 950.00 950.00 Kristallisationszeit (h) 12.00 12.00 12.00 H auptkristallphase Na4.8Y0.6Zr0.1La0.1Na 4.72 Y 0.96 N / a 4.62 Y 0.86 Zr 0.1 M g0.1 Al 0.1 Si 3.9 O 11.7 Al 0.10 Si 4.01 O 12 Al 0.1 Si 4.01 O 12 Side phases Na9YSi6O 18 Na3YSi3O9Na3YSi3O9n r <69 / n r>69 3.90 3.76 3.76 k 2.41 2.45 2.47 Conductivity at room temperature 2.15E-04 4.22E-04 2.76E-03 (S / cm) Table 3: Examples of implementation (continued) Example 52 53 54 Al2O3 0.74 0.72 0.72 B2O3 0.00 0.00 0.00 CaO 0.00 0.00 0.00 Fe2O3 0.00 0.00 0.00 Gd2O3 0.00 0.00 0.00 La2O3 0.74 0.00 0.00 MgO 0.00 1.45 1.45 Na2O 34.19 34.42 33.70 P2O5 0.00 0.00 0.00 SiO2 58.09 57.25 57.25 TiO2 0.00 0.00 0.00 Y2O3 6.25 6.16 5.43 ZrO2 0.00 0.00 1.45 Na / R 4.89 5.00 4.89 R / M 0.24 0.24 0.24 P / Si 0.00 0.00 0.00 P-Al -1.04 -1.03 -1.04 (P-Al)*0.2+1 <Na / R<(P-Al)*0.2+8 ja ja ja (P-Al)*0.2+4<Na / R<(P-Al)*0.2+7 ja ja ja Na / (Si+P-RE-Fe-Al) 1.55 1.58 1.50 Schmelztemperatur (°C) 1500.00 1500.00 1500.00 Kühltemperatur (°C) 580.00 580.00 580.00 Keimbildungstemperatur (°C) - - - Keimbildungszeit (h) - - - Kristallisationstemperatur (°C) 950.00 950.00 950.00 Kristallisationszeit (h) 12.00 12.00 12.00 Hauptkristallphase Na4.72Y0.86La0.1 Na4.83Y0.86Mg0.1 Na4.72Y0.76Zr0.1 A l 0.1 Si 4.01O 12 Al 0.1 Si 4.01 O 12 Mg 0.1 Al 0.1 Si 4.01 O 12 Side phases Na3YSi3O9Na9YSi6O 18 Na9YSi6O 18 n r <69 / n r>69 3.76 3.76 3.76 k 2.45 2.42 2.45 Conductivity at room temperature (S / cm) 2.80E-04 3.83E-05 2.12E-03 Table 3: Examples of implementation (continued) Example 55 56 57 Al2O3 0.72 0.73 0.72 B2O3 0.00 0.00 0.00 CaO 0.00 0.00 0.00 Fe2O3 0.00 0.00 0.00 Gd2O3 0.00 0.00 0.00 La2O3 0.72 0.00 0.00 MgO 1.45 1.46 1.43 Na2O 33.70 35.04 36.20 P2O5 0.00 1.46 1.43 SiO2 57.25 54.74 53.76 TiO2 0.00 0.00 0.00 Y2O3 4.71 5.11 5.02 ZrO2 1.45 1.46 1.43 Na / R 5.47 5.33 5.61 R / M 0.22 0.23 0.23 P / Si 0.00 0.05 0.05 P-Al -1.04 1.03 1.00 (P-Al)*0.2+1 <Na / R<(P-Al)*0.2+8 ja ja ja (P-Al)*0.2+4<Na / R<(P-Al)*0.2+7 ja ja ja Na / (Si+P-RE-Fe-Al) 1.45 1.52 1.60 Schmelztemperatur (°C) 1500.00 1500.00 1500.00 Kühltemperatur (°C) 580.00 580.00 580.00 Keimbildungstemperatur (°C) - - - Keimbildungszeit (h) - - - Kristallisationstemperatur (°C) 950.00 950.00 950.00 Kristallisationszeit (h) 12.00 12.00 12.00 Hauptkristallphase Na4.72Y0.66Zr0.1 Na4.84Y0.7Zr0.1 Na5.04Y0.7Zr0.1 La 0.1 Mg 0.1 Mg 0.1Mg0.1Al0.1Si4.01O12 Al0.1P0.2Si3.78O12 Al0.1P0.2Si3.74O12 Side Phases Na9YSi6O18 Na3YSi3O9 Na3YSi2O7 nr<69 / nr>69 3.76 3.95 3.95 k 2.45 2.44 2.41 Conductivity at room temperature (S / cm) 7.93E-04 8.65E-04 8.09E-04 Table 3: Examples of implementation (continued) Example V1 V2 V3 Al2O3 0.6 0.00 3.57 Na2O 25.40 28.13 32.14 P2O5 2.70 9.38 0.00 SiO2 43.30 37.50 57.14 TiO2 0.1 0.00 0.00 ZrO2 27.60 25.00 7.14 Na / R 1.76 2.25 4.50 R / M 0.59 0.44 0.25 P / Si 0.12 0.50 0 P-Al 3.27 13.64 -5.26 (P-Al) 0.2+1 < Na / R<(P-Al) 0.2+8 no no yes (P-Al) 0.2+4 < Na / R<(P-Al) 0.2+7 no no no Na / (Si+P-RE-Fe-Al) 1.07 1.00 1.29 Melting point (°C)>1600 not fusible 1600 Nucleation temperature (°C) Nucleation time (h) Crystallization temperature (°C) 910 950 Crystallization time (h) 12 12 Na3,7Al0,1Zr2Si3,1P0,4O12 Na3Zr1,33Si2PO12 Main crystal phase (NaSICon) (NaSICon) Na2ZrSi2O7 Secondary phase (much) ZrO2Na 14 Zr2Si 10 O 31 n r<69 / n r≥691.80 2.25 9.0 k 2.84 2.91 2.53 Conductivity at RT (S / cm) 10 -9 Table 4: Comparison examples

[0006] Example V4 V5 V6 Al2O30.00 1.04 0.00 N a2O 0.00 6.25 0.93P 2O5 27.23 38.54 41.24S iO2 13.39 6.25 1.86T iO2 35.72 47.92 51.85Z rO2 0.00 0.00 0.00A l2O3 1.34 0.00 4.13N a2O 22.32 0.00 0.00N a / R 2.18 5.29 8.15R / M 0.40 0.24 0.18 P / Si 0.75 0.26 0.07P -Al 18.86 6.85 2.51(P-Al) 0.2+1 < Na / R<(P-Al) 0.2+8no yes yes(P-Al) 0.2+4 < Na / R<(P-Al) 0.2+7no no noNa / (Si+P-RE-Fe-Al)0.91 1.68 1.83Melting temperature (°C)1600 1350 1350Nucleation temperature (°C) 600 570 K eimbildungszeit (h) 6 6 Crystallization temperature (°C) 850 800 800 Crystallization time (h) 12 6 6 Main crystal phase Na 4 Zr 2 Si 3 O 12 Na 3 YSi 3 O 9 Na 9 (Y, Gd)Si 5 O 18 Na2Si2O5 + unknown N ebenphase(much) ZrO2 phase proportion of main crystal phases.b. 81.6% nbnr<69 / nr≥692.5 5.0 5.0k3.02 2.46 2.3 Conductivity at RT (S / cm)nb 1.24E-09 nbTable 4: Comparative examples (continued) The invention is described below with reference to a figure. Fig. 1 shows in graphical representation the sodium ion conductivity (Y-axis, "Conductivity [S / cm]") of various glass-ceramic compositions as a function of their respective N5 volume percent in the crystal phase (X-axis, "N5 [Vol.%]"). As can be seen, for a conductivity of at least 10 -5 S / cm requires an N5 volume percentage of 55 vol% or more, preferably an N5 volume percentage of more than 60 vol%. The values ​​shown in the graph of Fig. 1 can be found in the following table: N5 vol% Na conductivity Reference numeral 7.4 2.22E-08 V7 32.4 5.78E-06 V8 60.1 1.06E-04 42 70.6 2.15E-04 49 78.4 4.25E-04 30 87.1 3.57E-03 32

Claims

Claims 1. Sodium ion conductor, in particular for use in a sodium ion or sodium solid-state battery, comprising more than 28 mol% Na2O and at least one crystalline phase, wherein the ratio nr<69 / nr≥69 of all at least divalent ions with an ionic radius less than 69 pm (n r<69 ) to all at least divalent ions with a radius of at least 69 pm (n r≥69 ), between 3 and 6.

2. Sodium ion conductor according to claim 1, having a sodium conductivity at room temperature of more than 10 -5 S / cm, preferably of more than 10 -4 S / cm, especially preferred by more than 10 -5 S / cm to 1 S / cm or from 10 -5S / cm to 0.5 S / cm.

3. Sodium ion conductor according to at least one of the preceding claims, having a mean cation charge of 2 < k < 3, preferably 2.2 ≤ k ≤ 2.8, particularly preferably 2.3 < k ≤ 2.6, calculated using the formula given in the description.

4. Sodium ion conductor according to at least one of the preceding claims, wherein at least 55%, preferably at least 70% of the crystal phase contains Na₅+q(R)(M)₄O₁₂ (R = divalent, trivalent, tetravalent, or pentavalent ions, M = Si, and optionally P or B), and preferably q ≥ 0.

5. Sodium ion conductor according to claim 4, wherein the trivalent ions are selected from the rare earth elements, aluminum and / or iron, and / or wherein the divalent ions are selected from Mg, Ca, Sr, Ba and / or Zn, and / or wherein the tetravalent ions are selected from Zr, Hf and / or Ti, and / or wherein the pentavalent ions are selected from tantalum and / or niobium. 6.Sodium ion conductors according to at least one of the preceding claims comprising (in mol%):. Na2O 28 - 60% RE2O3 0 - 15%, SiO2 35 - 75% P2O50 - 10% Al2O3 0 - 10%, MgO+CaO+SrO+BaO+ZnO 0 - 10%, B2O30 - 8% ZrO2+H fO20 - < 20 mol % TiO2 0 - < 20 mol % Fe2O30 - 18 %, Nb2O5+ Ta2O50 - 10 %, where RE2O3 represents the sum of the rare earth oxides.

7. Sodium ion conductor according to at least one of the preceding claims comprising (in mol%): Na2O 30-50%, RE2O3 1-10%, preferably 2-8%, SiO2 40-60%, P2O 50.1-8%, preferably 0.5-5%, Al2O3 0-5%, MgO+CaO+SrO+BaO+ZnO 0-5%, B2O30 - 5%, ZrO2+HfO2 0-<15 mol%, TiO2 0-<15 mol%, preferably 0-<5%, Fe2O30 - 15%, preferably 0-5%, Nb2O5+Ta2O5 0-5%, preferably free of Nb2O5 and / or Ta2O5, where RE2O3 represents the sum of the rare earth oxides.

8. Sodium ion conductor according to at least one of the preceding claims, wherein the rare earth oxides RE2O3 are selected from the group consisting of Y2O3, Gd2O3, Nd2O3, Pr2O3, La2O3 and Yb2O3 or combinations thereof.

9. Sodium ion conductor according to at least one of the preceding claims, comprising Al2O3+P2O5+B2O3 >0.1 mol%, preferably ≥ 1 mol% and particularly preferably <30 mol% or <20 mol% or <10 mol%.

10. Sodium ion conductor according to at least one of the preceding claims, wherein the cation ratio (P-Al) ∙ 0.2+ 1 < Na / R < (P-Al) ∙ 0.2+8, preferably (P-Al) ∙ 0.2 + 4 < Na / R < (P-Al) ∙ 0.2+7, wherein R represents the metal cations (RE, Al, Fe, Zr, Ti, Hf, Nb, Ta, Zn, Mg, Ca, Sr, Ba) and RE represents the rare earth cations, preferably selected from Y2O3, Gd2O3, Nd2O3, Pr2O3, La2O3 and Yb2O3 and / or combinations thereof.

11. Sodium ion conductor according to at least one of the preceding claims, wherein the ratio of Na to the sum of all cations R is: 1 ≤ Na / R ≤ 7, preferably 2.4 ≤ Na / R ≤ 6.8, where R represents RE, Al, Fe, Zr, Ti, Hf, Nb, Ta, Zn, Mg, Ca, Sr, Ba and / or combinations thereof. 12.Sodium ion conductor according to at least one of the preceding claims, wherein the ratio of metal cations R to non-metal cations M is: 0.1 ≤ R / M ≤ 0.4; preferably 0.2 ≤ R / M ≤ 0.3, where R represents RE, Al, Fe, Zr, Ti, Hf, Nb, Ta, Zn, Mg, Ca, Sr, Ba and M represents Si, P, B and / or combinations thereof.

13. Sodium ion conductor according to at least one of the preceding claims, wherein the ratio of the cations contained is Na / (Si+P-RE-Fe-Al) < 2.

14. Sodium ion conductor according to at least one of the preceding claims with P₂O₅ / SiO₂ < 1, preferably P₂O₅ / SiO₂ < 0.5, particularly preferably P₂O₅ / SiO₂ ≤ 0.

2.

15. Sodium ion conductor according to at least one of the preceding claims, which is substantially free of Sb, As, Te, V, Pb or Cd, of polyvalent ions and / or of Ga, Ge, Ta or W.

16. Sodium ion conductor according to at least one of the preceding claims, comprising at least one polyvalent component, preferably selected from Fe2O3. NiO, CuO, MnO2, CoO, TiO2 and V2O5, wherein the ratio of electronic conductivity to sodium ionic conductivity is < 10 -4 is, especially preferred <10 -317. Sodium ion conductor according to at least one of the preceding claims, containing less than 10 mol% of oxygen of various anions, in particular less than 10 mol% of halides, preferably < 5 mol%, particularly preferably < 2 mol%.

18. Sodium ion conductor according to at least one of the preceding claims, wherein the sodium ion conductor is a glass-ceramic ion conductor comprising at least one crystalline phase and at least one residual glass phase having a lower melting point than the crystalline phase. 19.A method for producing a sodium ion conductor according to any one of the preceding claims, comprising a melting process, preferably with the following steps: provision and mixing of the raw materials, melting of the raw materials at 1200-1650°C, preferably at 1300-1600°C, casting and cooling of the molten glass as a casting or ribbons, ceramicization, cold finishing of the glass ceramic, or milling to produce sodium ion-conducting powder.

20. Sodium ion-conducting powder comprising a sodium ion conductor according to at least one of claims 1 to 18, wherein the powder has a sintering temperature of less than 1050°C, preferably less than 1000°C.

21. Use of the sodium ion conductor according to at least one of claims 1 to 18 as a component of a sodium-ion battery or a sodium solid-state battery, or as an ion-selective membrane, or as a sensor.

22. Use of the sodium ion conductor according to claim 16 as a cathode material or as an additive to a cathode material in a sodium ion battery or a sodium solid-state battery.

23. Use of the sodium ion conductor according to at least one of claims 1 to 18 or of a sodium ion-conducting powder according to claim 20 for the manufacture of a sodium ion battery or a sodium solid-state battery.

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