1. Composite having a solid structure (10a), a silicate, lithium ions and at least one paramagnetic or diamagnetic element which is different from lithium, silicon and oxygen and is a transition metal ion, wherein the transition metal ion is a subgroup element of the seventh subgroup, wherein the solid structure (10a) has two regions (20) in which the solid structures (10a) form the same crystal orientation, characterized in that the regions (20) are arranged at a distance (30) of at least one millimeter from each other.

2. The composite according to claim 1, wherein the solid-state structure (10a) is at least partially formed as a single crystal of not less than one cubic millimeter, wherein the regions (20) are arranged within the single crystal.

3. The composite according to claim 1, wherein a portion of the quantity of lithium ions is movable within the solid state structure (10a) and into or out of the solid state structure (10a) by an external electromagnetic field.

4. The composite according to claim 1, characterized by a body side (40), wherein the two regions (20) are arranged directly on the body side (40).

5. The composite according to claim 1, prepared by a preparation process having processing steps, wherein the solid state structures (10a) constitute a growth direction (50), wherein the regions (20) are arranged perpendicular to the growth direction (50) by a distance (30) of at least 1 millimeter.

6. The composite according to claim 1, characterized in that the chemical composition is defined by at least one molar ratio, wherein the molar ratio is the quotient of the amount of the substance of the paramagnetic or diamagnetic element and the amount of the substance of the silicate, and in this case the molar ratio is less than 0.4.

7. Composite having a solid structure (10a), a silicate and lithium ions, wherein a portion of the amount of the lithium ions can move within the solid structure (10a) and into or out of the solid structure (10a) as a result of an external electromagnetic field and has at least one paramagnetic or diamagnetic element different from lithium, silicon and oxygen, wherein the solid structure (10a) has two regions (20) in which the solid structure (10a) forms the same crystal orientation, characterized in that the regions (20) are arranged at a distance (30) of at least one millimeter from one another.

8. The composite of claim 7, wherein the solid-state structure (10a) is at least partially formed as a single crystal of not less than one cubic millimeter, wherein the regions (20) are arranged within the single crystal.

9. The composite according to claim 7, characterized by a body side (40), wherein the two regions (20) are arranged directly on the body side (40).

10. The composite according to claim 7, prepared by a preparation process having processing steps, wherein the solid state structures (10a) constitute a growth direction (50), wherein the regions (20) are arranged perpendicular to the growth direction (50) by a distance (30) of at least 1 mm.

11. A composite according to claim 7, characterized in that the chemical composition is defined by at least one molar ratio, wherein the molar ratio is the quotient of the amount of the substance of the paramagnetic or diamagnetic element and the amount of the substance of the silicate, and in this case the molar ratio is less than 0.4.

12. A method having a quenching step that produces a solid state structure (10b) of a composite (60), the solid state structure (10b) of the composite (60) being different from an ambient temperature solid state structure, wherein the composite (60) has silicate, lithium ions, and elements other than lithium, silicon, and oxygen, the method being characterized by producing at least one gram of the composite (60) that is phase pure in the quenching step.

13. The method according to claim 12, wherein the heating process is performed in an oxygen-free atmosphere, wherein the final temperature of the heating process is the starting temperature of the quenching step, whereby the solid structure (10b) is homogeneous after the heating process.

14. The method according to claim 12, characterized in that the solid structure (10b) is prepared, the solid structure (10b) being formed directly below the melting temperature of the composite (60).

15. The method according to claim 12, characterized in that a Pmnb solid structure (10b) is formed in the quenching step.

16. Method according to claim 12, characterized in that the quenching step is carried out by means of a liquid (70).

17. The method of claim 16, wherein the composite (60) is cooled by a liquid (70) in direct contact with the composite.

18. The method of claim 12, wherein oxidation of the composite (60) is reduced or prevented by an oxygen absorbing article (80) during the quenching step.

19. The method of claim 12, wherein the compound (60) is cooled in the quenching step at least ten Kelvin (Kelvin) per second.

20. The method according to claim 12, characterized in that transition metal ions are used as elements, wherein elements of the eighth subgroup are used as the transition metal ions.

Background

Entitled "LiMPO₄And Li₂MSiO₄Christoph Neef, a paper of M ═ Mn, Fe, Co, growth and characterization of micro and macro crystals, "published by microwave-assisted hydrothermal synthesis (microwave-assisted hydrothermal synthesis) and optical floating zone (optical floating zone) techniquesPolyanionic LiMPO₄And Li₂MSiO₄Preparation of micro and macro crystals of M ═ compounds (Mn, Fe, Co). The prepared material is structurally characterized by a single crystal or powder X-ray diffractometer, metallurgy and chemistry, the morphology of the material is researched by a microscope and X-ray spectroscopy, and the material is further researched by electrochemical cycle, impedance spectroscopy, magnetic force analysis and mu spin (muon spin) and relaxation measurement (relaxation measurements). LiCoPO prepared by additive-assisted hydrothermal synthesis₄In particular, the significant impact of particle morphology on electrochemical properties and usability as a material for lithium ion batteries was determined. Two polycrystalline LiCoPO doped with Zn and Fe were further investigated₄The influence of the modification and transition metal substitution on the magnetic and electrochemical properties. The spin dynamics (spin dynamics) of the tetrahedral modification were studied with the help of nuclear magnetic resonance and μ SR. Thus, magnetic fluctuations (magnetic fluctuations) are also observed at high temperatures. LiMn is produced in a float zone technique at elevated pressure_1-xFe_xPO₄(x ═ 0, 0.1, 0.2, 0.3, 0.5, 1) and Li₂FeSiO₄And determining their exact growth parameters. For LiMn_{1- x}Fe_xPO₄The studies on the magnetic force characteristics and the electrical conductivity of lithium ions show that the magnetic ground state and the magnetic anisotropy of lithium ions and the high-temperature mobility of the anisotropy have significant doping dependence. Confirm the Li prepared₂FeSiO₄The single crystal structure of the modifier and the magnetic force characteristic of the modifier are studied for the first time.

Japanese patent application JP S59-141491, entitled "spodumene minerals", discloses crystalline complexes with lithium, silicate and manganese.

Japanese patent application JP S60-231499A entitled "production of a spodumene single crystal" discloses a production method utilizing a float zone technique.

PCT application WO 2011/162348 a1 entitled "silicic acid compound, positive electrode for secondary battery and method for producing secondary battery" discloses a method for producing silicic acid compound.

It is an object of the invention, inter alia, to provide a composite with improved material properties available, in particular improved properties in terms of scalability. According to the invention, this object is achieved by the features of claims 1, 7 and 12, while advantageous embodiments and further developments of the invention can be derived from the dependent claims.

Disclosure of Invention

The invention derives from a composite having a solid structure with two regions, a silicate, lithium ions and at least one paramagnetic or diamagnetic element different from lithium, silicon and oxygen, wherein the solid structure forms the same crystal orientation.

It is proposed to arrange the regions at a distance of at least one millimeter from each other. Thereby, the composite may have more favorable material properties and thus the cross section between the two regions is more likely to have the same crystal orientation, so that a composite may be formed which is monocrystalline in a cross section at least one millimeter in one direction of extension. Thus, the solid state structure of the composite can be more precisely defined by the preferred single crystal measurement method.

"complex having a solid structure, silicates, lithium ions and at least one paramagnetic or diamagnetic element" is understood to mean that the complex has: solid structure, (di) silicate, (tri) lithium ion, (tetra) at least one paramagnetic or diamagnetic component. Thus, the composite must have all four characteristics. The silicate, lithium ions and/or the element are preferably arranged in a solid structure. The silicate, lithium ions and/or elements preferably form at least partially or largely a solid structure. "silicate, lithium ion and/or element forms at least partially a solid structure" is understood to mean in particular that at least ten percent, in particular at least twenty percent, of the solid structure is formed by silicate, lithium ion and/or element. "silicate, lithium ion and/or the element preferably forms a solid structure to a large extent" is to be understood in particular to mean that at least 50%, in particular at least 70%, of the solid structure is composed of silicate, lithium ionAnd/or the elemental composition. The silicate, the lithium ion and the element each preferably have a mass of at least 0.1 g, in particular at least one g, alone or in combination. "solid state structure" is understood to mean a structure held together under ionic bonding, where it is based on the electrostatic attraction of oppositely charged ions. Solid-state structures are characterized in particular by a plurality of differently arranged lattices. The term "silicate" is understood to mean, in particular, a charged ionic solid compound consisting of oxygen and silicon element in bonded form. Silicates are formed in particular as nesosilicates, sorosilicates, cyclosilicates, inosilicates, phyllosilicates or tectosilicates. The silicate preferably has a tetrahedral solid structure and/or SiO₄In particular, silicates have a quadruple negative charge. The silicate preferably has SiO₄Tetrahedral solid structures, in which the silicates carry in particular a quadruple negative charge. A portion of the quantity of lithium ions may move within the solid state structure and/or enter or leave the solid state structure, preferably by an external electromagnetic field. "diamagnetic element" is understood to mean a material whose magnetic susceptibility χ is less than 0 or whose relative magnetic permeability χ is less than 1 in the pure material state. "paramagnetic component" is to be understood as meaning a material which, in the pure material state, has a positive susceptibility or a magnetic permeability of more than 1, with the aid of which a persistent magnetic order cannot be generated. "paramagnetic or diamagnetic component" is not to be understood as meaning a ferromagnetic component. "element" is understood to mean a chemical raw material which cannot be decomposed further by chemical means or a pure substance which cannot be decomposed further chemically. "region" is understood to mean a three-dimensional part of a solid-state structure which forms a volume of not less than one cubic micrometer and at most 0.001 cubic millimeter, wherein in particular the minimum extension in all three spatial directions is 1 micrometer and in particular the maximum extension in all three spatial directions is 0.1 millimeter. The volume is preferably not less than 100 cubic microns and/or at most 1000 cubic microns. "same crystal orientation" is understood to mean that one of the two regions is exclusively translated in such a way that its solid state structure coincides with that of the other region. It will also be appreciated that in addition,the main axis of the solid-state structure of one of the two regions differs from the in particular same main axis of the solid-state structure of the second region by at most 5 °, in particular by at most 1 °. Or again, it will be understood that alternatively, in measurements by means of a commercially available laue diffractometer, the principal axis reflectivity of one region cannot differ angularly from the other principal axis reflectivity of the second region. "principal axis reflection" is to be understood in particular as meaning the reflection of, for example, X-ray radiation which interferes with the solid structure depending on the principal axis of the solid structure. "principal axis" is to be understood to mean, in particular, an axis parallel to the normal orientation of the lattice planes of the solid-state structure. The solid-state structure particularly precisely forms the three main axes. "distance" is understood to mean the shortest connecting distance between two centers of mass of the respective regions. The element is preferably a transition metal ion. "transition metal ion" is understood to mean a charged subgroup element with an incomplete d-sub-shell. Alternatively or additionally, the "transition metal ion" is a zinc group element. Alternatively or additionally, the subgroup elements also include lanthanides and actinides. Since the element is a transition metal ion, the solid state structure may have a particularly advantageous regular solid state structure, which is particularly suitable for single crystal measurements. The transition metal ions are particularly and advantageously elements of subgroup seven. The transition metal ion is particularly preferably a manganese ion. Since the transition metal ion is a manganese ion, a particularly advantageous solid state structure can be prepared.

It is also proposed to form the solid-state structure at least partially, and in particular mostly, as a single crystal having a size of not less than one cubic millimeter, wherein the regions are arranged within the single crystal. "the solid-state structure is formed at least partially as a single crystal" is understood to mean that the solid-state structure is formed as a single crystal at least up to 10%, in particular at least up to 20%, advantageously at least up to 30%. "the solid-state structure is formed at least for the most part as a single crystal" is understood to mean that the solid-state structure is formed as a single crystal at least up to 50%, in particular at least up to 80%, advantageously at least up to 90%. "monocrystalline" is to be understood as meaning a solid material whose atoms or molecules are also arranged in a regularly repeating lattice structure over long distances. This also includes twins and products consisting essentially of single crystals. "bimorph" is understood to mean a crystalline material in which adjoining crystal lattices are arranged mirror-symmetrically to one another. By "the product mainly consists of a single crystal" is understood to mean that the product comprises at least 90% by weight of a single crystal, in particular consists of only one single crystal. However, double crystals and products mainly consisting of single crystals are preferably excluded. By means of an advantageous configuration, the composite has a single crystal at least in sections, wherein a very high material purity can be ensured in these cross sections, and the solid-state structures are arranged particularly regularly, whereby a particularly precise determination of the lattice constant of the solid-state structures can be achieved.

It is also proposed that the composite has a body side, wherein the two regions are arranged directly on the body side. "body side" is to be understood in particular as meaning the surface of the composite which is visible from exactly one viewing direction. "surface" is understood to mean the boundary surface of a three-dimensional object formed predominantly of a composite. "side" is understood to mean one or more surfaces that define the body and form the visible part of the surface of the body from one viewing direction. The composite has in particular at least two and/or at most six body sides. By this advantageous configuration, the measuring surface of the composite is improved, since not only one but both regions show a higher crystallinity. The measurement surface that the solid-state structure to be investigated can have is thus increased. This embodiment of the composite is therefore particularly suitable for surface measurements for determining the lattice constant of solid-state structures.

It is further proposed to prepare the composite in a preparation process having a process step in which the solid-state structures constitute a growth direction, wherein the regions are arranged perpendicular to the growth direction by a distance of at least one millimeter. "preparation process" is understood to mean a process having at least one process step. The preparation process preferably has at least two and in particular at least four process steps. The processing step is preferably characterized by an optical float zone technique. "optical float zone technique" is understood to mean a float zone technique by means of electromagnetic radiation. By "optical float zone technique" is understood to mean a process by melting, subsequent cooling and crystallization in order to form crystals, in which zone of the starting material either the molten zone or the starting material can be replaced, so that the whole starting material or a part thereof can be transferred into the crystals. The preparation process is characterized in particular by further preceding process steps, in particular at least two solid-state synthesis steps, in which the educts of the composite are prepared. A solid-state synthesis step is characterized in particular by at least two and preferably exactly three sintering steps. A processing step situated between the preceding solid-state synthesis step and the optical float zone technique comprises in particular at least one substrate ingot (substrate ingot) preparation step. "growth direction" is understood to mean the direction in which the solid structure grows during the processing steps, in particular the preparation of the solid structure. The technique of optically floating zones defining the growth direction is particularly preferred. By means of an advantageous embodiment, it can be assumed that it is very well possible to produce macroscopic single crystals, which will extend in particular perpendicularly to the growth direction.

The composite advantageously has a second element different from lithium, silicon, oxygen and a paramagnetic or diamagnetic element. The second element is preferably a transition metal ion. The transition metal ion is preferably a subgroup element of the eighth subgroup. The transition metal ion is particularly preferably an iron ion. By this advantageous embodiment, the composite is easier to prepare. The composite may be characterized by other elements than lithium, silicon, oxygen, paramagnetic or diamagnetic elements, and secondary elements, among others. The second element and/or in particular the further element can preferably be arranged within the solid structure and/or the second element and the further element form the solid structure, in particular at least partially and in particular to a large extent.

In another embodiment of the invention it is proposed that the composite has a chemical composition at least defined by a molar ratio, wherein the molar ratio is the quotient of the amount of the substance of the paramagnetic or diamagnetic element and the amount of the substance of the silicate. In this case, the molar ratio is less than 0.4, preferably less than 0.3, in particular greater than 0.1. "molar ratio" is understood to mean the quotient of the amounts of the substances. "quotient" is understood to mean a mathematical expression having a dividend and a divisor. "the molar ratio is the quotient of the amount of substance of the paramagnetic or diamagnetic element and the amount of substance of the silicate substance" is understood to mean, of the quotients, the dividend being the amount of substance of the paramagnetic or diamagnetic element and the divisor being the amount of substance of the silicate substance. By means of this particularly advantageous embodiment of the invention, a composite can be obtained with improved crystallinity properties, and therefore a particularly advantageous cross section with high material purity and high homogeneity in the composite.

All the aforementioned embodiments can be explicitly combined with one another.

In another aspect of the invention, the invention is based on a method having a quenching step that produces a solid state structure of a composite that is different from an ambient temperature solid state structure, wherein the composite has silicate, lithium ions, and an element that is different from lithium, silicon, and oxygen.

It is proposed to prepare at least one gram of phase pure complex in the quenching step. This process improves the efficiency of material utilization in the quenching step because, in particular, the proportion of scrap is reduced. The composite, which can be analyzed, for example, by neutron scattering experiments, can additionally be advantageously produced by this method, since it is of sufficiently high quality. In this way, in particular the atomic position can be measured directly, whereby a more precise determination of the solid-state structure can be achieved.

The "quenching step" is understood to mean a rapid cooling process of limited time, preferably less than one minute, during which the solid structure of the composite is prepared, unlike the solid structure at ambient temperature. "a solid structure of the composite produced which is different from the solid structure at ambient temperature" is to be understood as meaning in particular at least 10% by volume or 10% by weight, preferably at least 50% by volume or 50% by weight, of the solid structure which is different from the solid structure at ambient temperature. An "ambient temperature solid state structure" is understood to mean a solid state structure that has the lowest energy at ambient temperature. "ambient temperature" is understood to mean a temperature between 273 kelvin and 303 kelvin. By "preparing at least one gram of a phase-pure complex" is understood to mean that the complex firstly weighs at least one gram and secondly can be obtained in phase-pure form. "phase-pure" is understood to mean that the purity of the composite, in particular with respect to the external phase, is at least 95% by weight, in particular at least 99% by weight, and the solid structures in the composite are identical, at least 95% by volume, in particular at least 99% by volume. Alternatively, it will also be appreciated that no other phase can be determined by means of measurement by a commercially available XRD measurement device.

It is also proposed to prepare the solid structure directly below the melting temperature of the composite. "melting temperature" is understood to mean the temperature at which the liquid and solid phases of a material are at equilibrium, wherein the crystal lattice of the solid structure begins to change into a liquid state. "solid structure is prepared directly below the melting temperature of the composite" is to be understood in particular to mean that, for example, starting from the liquid phase during cooling, the solid structure is formed directly without a structural transformation from the solid state. By means of advantageous embodiments, solid-state structures can be produced which are capable of improving, for example, the ion mobility.

It is also proposed to use transition metal ions as elements. Since transition metal ions are used for the elements, particularly advantageous regular solid-state structures which are particularly suitable for single crystal measurements can be produced. Elements of the eighth subgroup are preferably used as transition metal ions. Iron ions are particularly preferably used as the transition metal ions. Since iron ions are used as transition metal ions, particularly advantageous homogeneous solid-state structures are produced. It is particularly preferred that the Pmnb solid structure is formed in the quenching step.

The quenching step is advantageously carried out with the aid of a liquid. "liquid" is understood to mean a substance which is in the physical state of a liquid at room temperature. The "quenching step is carried out with the aid of a liquid" is to be understood to mean that the liquid absorbs the thermal energy of the composite and is thus heated, so that an accelerated cooling process can be carried out compared to a cooling process without a liquid. Preferably, the compound is cooled by direct contact with a liquid. By this advantageous embodiment, the quenching step can be carried out particularly quickly, so that a high cooling rate can be achieved. In addition, the use of a liquid makes possible a high heat transfer from the compound to the liquid; this is based on the high heat capacity of the liquid. Water and/or oil are particularly used as the liquid.

It is further proposed that the oxidation of the composite is reduced or prevented in the quenching step by means of the oxygen-absorbing article. "Oxidation" is understood to mean the emission of electrons from elemental and/or chemical bonds. By "oxygen absorbing article" is understood a composite or device which absorbs oxygen during the quenching step, thereby producing a reduced oxygen environment, particularly within a close range of the product, e.g., ten centimeters. By "reducing or preventing oxidation of the composite" is understood to mean that the oxygen content in the composite is lower than the content of the non-oxygen absorbing article. The difference is at least 10%, in particular at least 20%. By means of this advantageous embodiment, the quenching step makes particularly efficient use of the material, so that particularly little scrap is produced in the quenching step.

In another embodiment of the invention it is proposed to cool the composite in the quenching step at a rate of at least ten kelvin per second. In this way, particularly pure solid structures can be produced, while particularly solid structures which form just below the melting temperature can be produced.

It is further suggested that the method has a heating process performed in an oxygen-free atmosphere, wherein the final temperature of the heating process is the starting temperature of the quenching step, so that the solid structure is homogeneous after heating. The "heating process" is understood to mean a process of increasing the temperature. "oxygen-free atmosphere" is understood to mean a gaseous composition having a maximum of 1% oxygen, in particular a maximum of 0.01% oxygen. "homogeneous" is understood to mean that the solid structure likewise amounts to at least 95% by weight, in particular at least 99% by weight, and/or at least 95% by volume, in particular at least 99% by volume.

In another embodiment of the invention, it is proposed to prepare the composite by a method characterized by a quenching step.

All the aforementioned embodiments can be explicitly combined with one another.

For the purpose of explaining the present patent application, terms may also be explained using prior art papers.

Batteries, secondary batteries, optical devices, jewelry, sample crystals, surface coatings of devices and/or electronic components, such as are disclosed in DE 3433150C2 of Ludwig Rausch, may have a composite according to the invention, or these components may in particular be produced by a method according to the invention. However, other intended purposes are not excluded. It is particularly conceivable that a product which meets the above-mentioned intended purpose can be manufactured from the composite in a further method step. It is particularly envisaged that the process has other preparation steps not claimed in the present patent application, so as to obtain a product that can meet the intended purposes described above.

Other advantages are obtained from the following description of the figures. Embodiments of the invention are shown in the drawings. The figures, description and claims include many combinations of features. Those skilled in the art will also actually consider these features separately and combine them into further useful combinations.