EP3710405A1

EP3710405A1 - Process for solid synthesis of mixed metal oxides, and surface modification of said materials and use of said materials in batteries, in particular as cathode materials

Info

Publication number: EP3710405A1
Application number: EP18807036.1A
Authority: EP
Inventors: Werner Lautenschläger; jens Lautenschläger; Sebastian Oberwalder
Original assignee: Iontech Systems AG
Current assignee: Iontech Systems AG
Priority date: 2017-11-17
Filing date: 2018-11-16
Publication date: 2020-09-23
Also published as: DE102017220619A1; US12030788B2; WO2019096967A1; US20200385283A1; CN111655625A

Abstract

The present invention relates to a process for producing mixed metal oxide particles, in which particles from parent compounds are converted by contactless energy input. The invention also relates to a process for coating bodies, preferably transition metal- or metal particles, transition metal- or metal oxide particles, transition metal- or mixed metal oxide particles, or silicon- or sulphur particles, especially preferably particles having a mass of less than one milligram and being in the form of grains, fibres, hollow fibres, or 2D structures, by heating with the exclusion of oxygen in the presence of a carbon source.

Description

Process for the solid synthesis of metal mixed oxides and surface modification of these materials and use of these materials in batteries, in particular as cathode materials

Summary

The invention relates to a synthesis process for the preparation of metal mixed oxides, preferably transition metal mixed oxides, particularly suitable for use in batteries. The synthesis is carried out by contactless energy input, preferably by electromagnetic radiation, and particularly preferably by microwave radiation. For this purpose, the starting materials are present as pre-shredded particles in the stoichiometric ratio. The starting metals are preferably present as salts, particularly preferably as acetates.

The metal mixed oxides prepared according to the invention are further processed in stages for use in batteries, in particular surface-coated with a special process. The surface coating is carried out by providing a suitable carbon source and non-contact energy input, preferably by electromagnetic radiation, and particularly preferably with microwave radiation.

For use in batteries, it is preferable to integrate electrolytes, in particular solid electrolytes, directly into the cathode materials or on their surfaces, as part of the material synthesis.

Likewise, further processing steps may be expedient, such as in particular etching (etching) for the production of multiphase materials and quenching to improve the internal homogeneity.

Finally, the materials produced according to the invention can be the basis of a novel battery production technology in which the manufacture of the batteries can be carried out without the presence of (alkaline) alkali metals. As a result, these materials are independent of the type of cation source used and thus equally suitable for a variety of different cation sources, which in particular brings significant cost savings and processing advantages.

In a particularly preferred embodiment, doped nickel-manganese-cobalt (NMC) battery materials are disclosed, which are particularly suitable for processing with cheaper (alkaline) alkali metals. In a particularly preferred embodiment, the processing of the base material takes place alkali-free, with the addition of sodium only during battery formation.

description

State of the art

In the prior art, the production of metal mixed oxides, in particular of battery materials, usually wet-chemical takes place. The dissolved salts of the corresponding metals are mixed in the desired ratios and brought to (common) crystallization. In most cases, the environment is controlled by the addition of chemicals pH. The resulting crystallization products are then precipitated by addition of other chemicals. This is followed by further usually complicated separation, cleaning, washing and comminution / milling processes. Subsequently, residual water and / or impurities are removed by drying or heating. Finally, by a firing / calcination step, the salt residues are substituted by oxygen and the materials are converted to their oxide state. As a rule, further processing steps are necessary thereafter, in particular comminution / grinding processes.

For surface coating of the materials thus produced are in the prior art predominantly mechanical processes such as drum coating, and mechanical-thermal combination processes such as drum coating under Heating and addition of additional materials and reaction chemicals used.

Further processing into batteries also takes place in the prior art by wet-chemical means, in particular by suspension coating (slurry coating) processes.

In the prior art, electrolytes are generally likewise added in liquid form, for example as (standard) liquid electrolytes, or as a suspension of solid electrolytes.

Also, in the prior art, a subsequent addition of the cation source is not effectively possible, which is why it must already be added as part of the metal oxide. This requires not only increased manufacturing costs, but also manufacturing problems such as production losses of Fithium in heating / calcining. This is associated with additional costs, u.a. due to the necessity of the use of (considerable) material surpluses also corresponding recovery or environmental problems. In addition, a use of different cation sources with the same base material is not possible, or is generally a use of sources other than Fithium afflicted with considerable difficulties.

The present invention provides a route to dry synthesis that eliminates the need for wet chemicals and solvents, resulting in significant cost and environmental benefits. Likewise, the number of necessary process steps can be significantly reduced, which offers further significant cost advantages.

The process according to the invention also proves to be superior in terms of further processability in that, surprisingly, the material produced according to the invention can be directly equipped with solid electrolytes, which can be added later to the electrolytes and optionally also to the wet-chemical suspension coating (slurry coating) process makes unnecessary, or at least leads to a significant reduction of the necessary additional chemicals (such as binders). Likewise, surprisingly, it is possible to add the cation source only later as part of the battery forming process.

Furthermore, methods are provided for further processing of the materials according to the invention for use in batteries, in particular as cathode materials, which likewise stand out from the prior art by a reduction of the process steps and used process chemicals and the resulting cost savings and / or technically superior materials.

Finally, in a particularly preferred embodiment, the invention provides specific dopant materials for battery materials, particularly nickel manganese cobalt cathode materials ("NMC materials"), which greatly facilitate the use of cation sources other than lithium, particularly sodium, magnesium and aluminum.

Description of the invention

The present invention provides a process for the preparation of mixed metal oxide particles in which particles are reacted from starting compounds by non-contact energy input.

For the purposes of this invention, a mixed metal oxide (metal mixed oxide) or transition metal mixed oxide is a mixed metal oxide comprising two or more (transition) metals. Preferably, a mixed metal oxide comprises three or more (transition) metals, more preferably three to six (transition) metals, more preferably four or more (transition) metals, and most preferably four or five (transition) metals. Particularly preferably, a transition metal mixed oxide comprises 1 to 4 transition metals. Optionally, a mixed metal oxide or transition metal mixed oxide may also comprise a nonmetal such as phosphorus, especially if only one or two metals are included (eg LiFePO ₄ or the like).

Preferably, a mixed metal oxide produced by the process of the present invention comprises at least one transition metal selected from the group consisting of titanium, vanadium, manganese, iron, cobalt, nickel, yttrium, zinc, silver, and cadmium. Particularly preferred is at least one transition metal selected from the group consisting of manganese, iron, cobalt, nickel, and yttrium.

Particularly preferably, a mixed metal oxide comprises at least one alkali or alkaline earth metal, and / or aluminum, and / or tin. Preferably, the alkali or alkaline earth metal is selected from lithium, sodium, potassium and magnesium.

Preferred mixed metal oxides include nickel, manganese and cobalt, preferably in combination with lithium, sodium, magnesium and / or aluminum.

Other preferred mixed metal oxides include cobalt, nickel, manganese, and yttrium, preferably in combination with lithium or sodium. Other preferred mixed metal oxides include iron and lithium in combination with phosphorus.

For the purposes of this invention, a mixed metal oxide or transition metal mixed oxide preferably comprises at least one (transition) metal oxide and at least one further element, which may also be an alkali metal or alkaline earth metal or a nonmetal. Preferably, the mixed oxide comprises two to five elements plus oxygen, more preferably at least one transition metal and at least one (alkaline) alkali metal plus oxygen.

Examples of particularly preferred mixed metal oxides comprising a transition metal and an alkali metal include LiCoO ₂ , LiCoO ₂ , LiNiO ₂ , LiMnO ₂ and Li ₄ Ti ₅ O ₂ , as well as spinels such as LiMn ₂ O ₄ , and the like.

Examples of particularly preferred mixed metal oxides comprising two or more transition metals and an alkali metal include LiNi _x Co _x O ₂ (with 0 <c <1), Li [Ni _Xa MnyaCoza] 0 ₂ (where xa + ya + za = 1, eg LiNio, 33Coo, 33Mno, 3302), LiNio, 85Coo, iAlo, o502, Na [Ni _Xa Mn _ya Co _Za Yxb] 02 (where xa + ya + za + xb = 1, eg Na [Nio, 58Mno, 32Coo, o92Yo, oo8] 0 ₂ ), and the like.

Examples which additionally comprise a nonmetal include LiFePC, LiFeYPO ₄ and the like.

The starting compounds are preferably salts of the corresponding metals (for example, acetate salts or acetate salt hydrates) provided as particles in the stoichiometric ratio required for the desired product.

The particles of the starting compounds preferably have a particle size of up to a few millimeters, for example 10 mm or smaller, more preferably 5 mm or smaller, more preferably 2 mm or smaller, more preferably 1 mm or smaller, and particularly preferably 0.5 mm or smaller..

Preferably, the synthesis of the desired mixed metal oxides takes place in that the starting materials to particles having a particle size of 250 microns or smaller (<250pm), more preferably of 100 microns or smaller (<100pm), more preferably of 50 pm or less (< 50pm), more preferably twenty microns or smaller (<20pm), more preferably ten microns or less (<10pm), more preferably one micron or less (<1pm), and most preferably 0, 1pm or less (<0). lpm), or particles are provided with this particle size, and then initiated by contactless energy input, a synthesis of these particles.

If particles of the starting compounds with particle sizes greater than 250 pm are used, an additional treatment step may be required to prepare mixed metal oxide particles suitable for battery applications. A preferred example of such a treatment is, for example. a homogenization step, for example by treatment with an Ultratorrax mixer, by treatment with ultrasound in solution, or the like. The necessary additional steps for washing out / rinsing or separation / filtration increase the effort and cost of the synthesis. For example, they may also be associated with disadvantages such as increased energy expenditure, wastewater problems, solvent disposal, detoxification of vapors, etc.

The size of the particles of the starting compounds can be adjusted by sieving, for example. Particle size measurement may also be performed optically, optionally using appropriate (e.g., microscopic or electron microscopic) magnification.

In the process according to the invention, the particles of the starting compounds can be used with or without additional solvents, catalysts or other process aids, preferably without. The process according to the invention is particularly preferably carried out as a solid-state reaction, in particular as a dry solid-state reaction. As a result of the fact that the energy input takes place without contact, the inventive method neither precipitates the starting materials at a specific heat source, nor does the particles cake significantly larger units / lumps or even a melt. In a particularly preferred embodiment, the particles of the starting compound are used in the form of a dry mixture of separate particles from in each case one starting compound, wherein the individual particles are not interconnected, agglomerated, aggregated, compressed or the like.

In order to achieve the desired end product, the particles of the starting compounds must be small enough. For this purpose, a comminution to the orders of magnitude described above is required. Preferred crushing method is the use of eddy current mills (Jet Mill). In order to achieve particularly small particle sizes, it is possible in a preliminary step as hydrates provided starting materials (for example: cobalt (II) acetate tetrahydrate, nickel (II) acetate tetrahydrate, manganese (II) - acetate tetrahydrate, manganese (III) Acetate dihydrate, lithium acetate dihydrate), after initial comminution (eg, to about one hundred microns (100pm)) to dehydrate, making these materials porous, and particularly suitable for a further comminution are suitable. Alternatively or additionally, the materials can also be calcined, ie the salts are converted by heating with elimination of the volatile counterion in the oxide form. The dehydrogenation and / or calcining can be carried out by any known method, in particular by heating with contactless energy input, more preferably by microwave input under negative pressure. The resulting porous materials can then be facilitated further reduced, resulting in a particularly small particle size can result. At the same time, very good mixing of the particles takes place in the eddy current mill when, as is preferred, all the metals or metal salts are already ground together.

For this purpose, the particles are preferably provided in the desired direct stoichiometric ratio of the desired products.

The energy input must be contactless. Preferred method is irradiation with electromagnetic radiation, in particular with a wavelength of 200 nm to 50 cm. Particularly preferred here is the use of a microwave source which directly excites the metal particles. Suitable microwave sources are magnetrons that emit microwave radiation in the wavelength range of 1 cm to 50 cm (600 MHz to 30 GHz) with a power of 20 to 2000 watts. For example, standard magnetrons can be used, for example, at a power of 500 to 1000 watts microwaves with a wavelength of about 12 cm (2.45 GHz, 2.455 GHz, 2.46 GHz) or with a wavelength of about 30 cm (860 MHz, 915 MHz). Alternatively, lasers, electromagnetic induction or electron beams are basically also suitable as energy sources, with electron beams and lasers being less costly as expensive energy sources, and possibly having to use different starting materials in the case of electromagnetic induction, which can likewise have a negative effect on the economy. Examples of lasers are CO / CO ₂ lasers or solid lasers, preferably diode lasers, for example a neodymium-doped yttrium aluminum garnet laser (Nd: YAG). Due to the non-contact entry, the energy is transferred directly to the individual particles, or the heating proceeds directly from them by coupling the shaft. The number of impacts necessary for the synthesis is (only) reached where it is needed. Thus, there is no caking of the synthesis products, and subsequent re-grinding is basically not necessary (depending on the intended use). The preferred particle size of the final products is 20 microns or smaller, more preferably 10 microns or smaller, and most preferably 1 micron or smaller.

The energy input preferably takes place with constant movement of the particles, for example by stirring and / or rotation of the reaction vessel and / or passing through an inclined plane.

Preferably, the starting materials are present as solids comprising vaporizable fractions, more preferably as salts. Among the salts, acetates are particularly preferred. The salts are more preferably in the form of hydrates (for example: cobalt (II) acetate tetrahydrate, nickel (II) acetate tetrahydrate, manganese (II) acetate tetrahydrate, manganese (III) acetate dihydrate, lithium acetate dihydrate ). Equally possible is the reaction of other salts, such as carbonates to acetates as a precursor of the same process possible (eg: L1 ₂ CO ₃ + 2 CH ₃ COOH -> 2 CH ₃ COOL1 + CO ₂ + H ₂ O), preferably supported by contactless entry of reaction energy, for example by microwave radiation.

Due to the use of these relatively large molecules, only a (relatively) small number of metal atoms per particle are present in the preferred comminution region, resulting in a very good homogeneity of the end product. Likewise, the metal atoms in the preferred compounds only a small proportion of the total material or total molecule, which is why after evaporation of the volatile components (= dehydration and thermal decomposition of the salts), a porous body is formed, which is both excellent for further comminution (see above) as well as reaction or fusion with other metals in close proximity. As described, this dehydrogenation and thermal decomposition preferably takes place by contactless input of energy, more preferably by uniform pointwise heating with microwave radiation.

The loss of size due to dehydration / decomposition also compensates for particle growth by fusing particles, which is why the end products of the process generally have about the same particle size as the starting materials. Likewise, this results in very large and extremely reactive surfaces, which further promotes both the efficiency of the reaction itself, as well as their closely localized sequence. Finally, the porosity of the particles due to the thermal decomposition offers further, in part very surprising advantages.

In particular, the presence of these internal cavities allows the integration of an electrolyte, preferably a solid electrolyte and / or an organo-gel electrolyte, directly into the particles. For this purpose, the solid electrolyte can already be provided during the synthesis in a suitable form-also as a combination of precursor substances-as well as applied (directly) after completion of the synthesis in a further process step with contactless energy input. Organo-gel electrolytes are applied after completion of the synthesis. Preferred solid electrolytes are in particular Lithim-rich Antiperovskite (lithium rich anti-Perovskites, such as: Li ₃ OBr or Li ₃ OCl), boron hydrides (such as: BH ₄ , for example: LiBH ₄ , NaBH ₄ ) and lithium salts with sulfur-containing anions, in particular Li ₂ S or Li ₃ PS ₄ , as well as lithium phosphate nitrate (Li ₃ P0 ₄ N).

Preferred organo-gel electrolytes are cyano resins such as PVA-CN in ECiEMC / LiPF _ö / FEC, said PVA-CN = cyanoethyl polyvinyl alcohol; EC = ethylene carbonate; EMC = ethyl methyl carbonate; LiPFo = lithium hexafluorophosphate; FEC = fluoroethylene carbonate.

Basically, a coating or fusion of solid electrolytes with non-inventively prepared (metal oxide) - Particles or microwave-reflective bodies of all kinds with contactless energy input possible, which is why this coating or fusion is claimed both in combination with the subject invention materials and independently.

The direct integration of solid electrolytes in battery materials significantly reduces the risk of fire compared to the prior art. Similarly, with the integration of a solid electrolyte, a significant reduction of conductive additives is possible and desirable due to the improved conductivity. These additive reductions lead to a significant cost reduction, as well as to a significant increase in the capacity of the batteries thus produced in comparison with the prior art.

If a porous structure of the particles is undesirable, or as soon as all other substances have been introduced into the cavities, the porous structure can be prevented or destroyed by internal compression processes (quenching) of the material. For this purpose, a rapid cooling of the surface after the synthesis or a constant cooling of the environment during the synthesis, whereby the surface remains significantly colder or cools much faster than the core, and thus there is an internal compression (quenching) of the material. Here, the advantage is exploited that due to the contactless energy input takes place only a one-off heating, and thus a cooling both during the process is possible without significantly affecting the process, and the energy expenditure remains justifiable. Quenching preferably takes place by supplying (relatively) cool gas or transferring the hot particles into a microwave-transparent liquid which is present at room temperature (about 20 ° C.). Depending on the desired further processing, however, it may be desirable to dispense with this step in order to utilize the nanoporous structure for further process steps or to carry out the step of internal compression only at a later point in time of the entire production process. Another processing step, which can be done either at this point in the process or at a later time, or can be completely omitted, is the etching (etching) of the particles. This serves in particular to achieve a phase transition or layer structure within the produced particles, for example in the preferred NMC cathode materials. In this case, for example, lithium is removed from a lithium-nickel-manganese-cobalt oxide from the outer layers of the particles. This is preferably done by heating the particles, preferably by non-contact energy input / microwave, in a suitable reactive atmosphere of an inert gas such as argon, and a reactive gas such as ammonia (NH ₃ ) and / or sulfur hexafluoride (SF _Ö ). Particularly preferably, the reactive atmosphere comprises the reactive gas in low concentrations (eg Ar 98% SF ₆ 2%), since the reaction can proceed strongly exothermic.

The metal mixed oxide particles produced according to the invention are preferably coated with a carbon layer after their preparation (and optionally with addition of electrolyte and / or quenching and / or etching).

This coating can be carried out in direct connection to the first synthesis step by bringing the already heated / heated particles into contact with a carbon source in the absence of oxygen. The oxygen exclusion can be achieved by a protective atmosphere or by reaction in a liquid. Preferably, the under constant movement of the particles, for example by stirring and / or rotation of the reaction vessel and / or passing through an inclined plane takes place. The coating is preferably carried out with further heating by non-contact energy input with electromagnetic radiation from the microwave range to the high-frequency range (wavelength 200 nm to 50 cm), more preferably by microwave radiation in the range of 1 to 50 cm. Likewise, the particles can be heated separately or independently of the first step, again preferably by contactless energy input as just described. Not only the particles according to the invention, but also all bodies, preferably differently produced particles, grains, fibers, hollow fibers or 2D structures, preferably those having a mass of one milligram or less, more preferably those having a mass of one hundred micrograms or less, are coated by this method. In addition to the materials according to the invention, a coating of silicon (Si), sulfur (S), semimetals (examples of semimetals are silicon, germanium, arsenic and the like), transition metals (examples of transition metals are nickel, manganese, cobalt, iron, copper, Zinc, vanadium, yttrium, silver, niobium, titanium, cadmium and the like, preferably nickel, manganese, cobalt and iron) and metals (examples of metals are aluminum, tin and possibly gallium, lead, bismuth and the like) and / or their Oxides or a combination of two or more of these materials, with silicon, sulfur and oxides of the transition metals being particularly preferred. In addition, the coating process according to the invention can of course also be carried out with mixed oxide particles which have not been prepared by the production process according to the invention. Because of this possibility of independent surface treatment, the present process is claimed both in combination with the basic synthesis and independently.

Preferably, the carbon source is in the form of a hydrocarbon source, preferably liquid or gaseous, more preferably a microwave transparent compound. Particular preference is given individually or in combination with one another: liquid: pentane, hexane, heptane, octane, nonane, decane, including all isomers, for example n-hexane, 2-methylpentane, and all cyclic forms, for example cyclohexane or gaseous: methane, ethane , Propane, n-butane and iso-butane. Gases are preferably present as part of an oxygen-free mixture with nitrogen and / or argon and / or hydrogen, for example: propane 5% hydrogen 2% argon 93%.

In a preferred embodiment, the particles to be coated are dispersed in the hydrocarbon source. For example, the particles to be coated can be dispersed in a liquid or gaseous hydrocarbon source with constant movement of the particles. By heating the particles, preferably selectively by non-contact energy input with microwave, it comes to the thermal dissociation of hydrocarbons. Since this takes place directly on the particle surface, the accumulation of the liberated carbon on the particle surface continues. This is supported by the reductive effect of the liberated hydrogen, or of the additional hydrogen present in the protective atmosphere.

Particularly advantageous is the effect that only a short-term selective heating takes place with contactless heating of the particles under motion, which is why only the energy necessary for the reaction is achieved, but not beyond that to a melt of the particles or a fusion of different particles or even a clumping of the material or an attachment of the material comes to the surfaces of the reaction vessel.

Further particularly advantageous when using microwave radiation is that the microwave heats only the particles, but not the carbon source. This allows the process to proceed at moderate ambient temperatures, for example in a cyclohexane bath with a liquid temperature significantly below the boiling point. This hardly leads to undesirable losses of the carbon source. Nevertheless, small quantities which evaporate below the boiling point can easily be enclosed in a closed vessel without risking the development of a particular overpressure, and recovery from the then very cool exhaust air is also easily possible. Likewise, the accumulated carbon is not or only very badly heated. This leads to the formation of the carbon layer being hindered or slowed down by already existing carbon deposits, which results in a very homogeneous and very thin coating. Such thin homogeneous coatings are particularly suitable for technical applications, in particular as battery materials. For example, a very thin carbon coating leads to significant savings of conductive additives and cathode volume, for example in the case of cathode materials Significant cost savings also leads to a significant increase in volumetric capacity.

Likewise, the particles can be coated by means of this method not only with carbon, but also with other materials targeted, for example, with silicon and the like, and in particular with solid electrolytes or their precursors. Preferred examples are, for example, Li ₂ S, Li ₃ OBr or Li ₃ OCl, boron hydrides (eg BH ₄ , for example: LiBH ₄ , NaBH ₄ ) and Li ₃ PO ₄ N and the like.

The use of all described subject matter in batteries (e.g., primary cells, secondary cells, and the like) and / or electrochemical systems of all types is expressly recited.

Due to its porous structure and / or the integration of (solid electrolyte directly into the particles, the material according to the invention can remain free of alkali or alkaline-earth metals during the stack / cell / battery production process The process architecture and cost savings, makes the present technology also with regard to the cation source used (= the alkali metal or alkaline earth metal used) independent Batteries of the invention can thus use any one or more different alkali or alkaline earth metal , "Divalent" or "trivalent", preferably selected from: lithium (Li ⁺ ), sodium (Na ⁺ ) or potassium (K ⁺ ) as monovalent ion, magnesium (Mg ²⁺ ) as divalent or aluminum (Al ³⁺ As a trivalent ion, very particularly preferably: lithium, sodium or magnesium The selected ions are preferably used in the Frame of the cell or battery stack molding process as "liquid A" injected into the cathode. The liquid A is preferably a solution of a salt of the metal in a suitable solvent, preferably water or dimethyl sulfoxide (DMSO).

Preference is given in connection with the use of other (alkaline) alkali metals than lithium and the doping of the materials with transition metals with a larger atomic radius, for example, with yttrium, preferably in the proportion of starting material of 90% or greater, to a proportion of yttrium of 10% or smaller. The doping is preferably carried out by simultaneous synthesis according to one of the methods described above.

The implementation of the injection process per se corresponds to the state of the art for such processes, and can be carried out in any of the embodiments used as standard for such processes. The selection of the appropriate process will usually be made in adaptation to the existing or desired production plant.

Preference is given to a production method in which initially an alkali and alkaline earth-free battery precursor cell is produced, into which subsequently liquid sources of alkali (or alkaline earth) ions are pumped. Preferably, each cell chamber is separately supplied with the alkali ion source, with the liquid circulating through appropriate inlet and outlet ports until the appropriate cell parameters are achieved. For this purpose, one or more of the following parameters are preferably measured at the respective poles or ports and optionally influenced / varied in a suitable manner: voltage, temperature, pressure, impedance, molarity / concentration and flow rates of the fluid A (preferably both at the inlet and outlet ports) also outlet). Since this manufacturing method is not limited to the subject battery, but is suitable for a variety of types of batteries, this is claimed both in combination with the subject battery, as well as independently.

Examples

example 1

In a microwave rotary evaporator (Rota-Prep, MWT AG, 12.2 cm / 2.455 GHz) are pre-crushed to particle sizes smaller than 10 microns: 2.99 g cobalt (II) acetate tetrahydrate, 12, 44g nickel (II) acetate - Tetrahydrate, 7.35 g of manganese (II) acetate tetrahydrate, 2.70 g of yttrium (III) acetate tetrahydrate and 11.0 g of lithium acetate dihydrate. These particles are heated with rotation (rotational speed about 1 Hz / 60 rpm) for 10 minutes with a microwave power of constant 500 watts. Escaping water / acetate is sucked off, fresh air tracked. The resulting material is processed by standard methods to battery cells.

Example 2

As in Example 1, but additionally 8.4 g of lithium chloride and 5.9 g of lithium oxide, also pre-reduced to particle sizes less than 10 micrometers presented, the microwave power is increased to 700 watts. When further processing to a battery can be dispensed with the addition of an electrolyte.

Example 3

Instead of further processing the material resulting from Example 1 directly into batteries, 100 ml of cyclohexane are added after heating for 10 minutes. The particles are then heated for a further 10 minutes with a microwave power of 500 watts to coat them with carbon.

Example 4

As Example 1, but without the presentation of lithium acetate dihydrate. Immediately after completion of the microwave heating 20 g of 2% (by weight) PVA-CN are dissolved in 1: 2 (v) EC: EMC / LiPF _ö / FEC, said PVA-CN = cyanoethyl polyvinyl alcohol, EC = ethylene carbonate; EMC = ethyl methyl carbonate; LiPF _ö = lithium; FEC = fluoroethylene carbonate added. This is followed by another microwave heating for 2 minutes with a power of 500 watts. When further processing to a battery can be dispensed with the addition of an electrolyte. The battery is made so that the cathode forms a separate chamber separate from the anode. In this chamber, under application of an external charging voltage of 4.6 V, a 10% solution of Lithium chloride initiated in DMSO. This solution circulates through an inlet and outlet for a period of 3 hours.

Claims

claims

1. A process for the preparation of mixed metal oxide particles, are reacted in the particles of starting compounds by contactless energy input.

2. The method of claim 1, wherein the starting materials in the desired stoichiometric ratio as particles having a size of two hundred and fifty microns or smaller (<250pm), more preferably one hundred microns or smaller (<l00pm), more preferably of 50 pm or less (< 50pm), more preferably twenty microns or less (<20pm), more preferably ten microns or less (<10pm), more preferably one micron or less (<1pm), more preferably 0.1pm or less (<0, 1pm) , are provided, and then initiated by contactless energy input, a synthesis of these particles.

3. The method of claim 1 or 2, wherein the energy input is effected by electromagnetic radiation of a wavelength of 200nm to 50cm, preferably by microwave radiation having a wavelength of 1 to 50 cm.

4. The method according to any one of the preceding claims, wherein the

Starting materials are provided as salts, preferably as acetates, more preferably as acetate hydrates.

5. The method of claim 4, wherein the starting materials are dehydrogenated and / or calcined after pre-crushing to less than 100 microns, and then further comminuted, preferably using an eddy-current mill.

6. The method according to any one of the preceding claims, wherein the

Energy input under constant movement of the particles is carried out, preferably by stirring and / or rotation of the reaction vessel and / or passing through an inclined plane.

7. A process for the production of particles in which transition metal or metal

Oxides or mixed oxides or silicon or sulfur in the desired stoichiometric ratio with one or more solid electrolytes or solid electrolyte precursors as particles having a size of fifty microns or less (<50pm), preferably ten microns or less (<10pm), more preferably one micrometer or less (<1 mih), and then by non-contact energy input, synthesis of these particles or coating of the transition metal or metal oxides or mixed oxides or silicon or sulfur with the solid electrolyte (s) is initiated.

8. Process for the preparation of particles in which transition metal or metal

Oxides or mixed oxides or silicon or sulfur in the desired stoichiometric ratio with one or more organo-gel electrolytes or organo-gel electrolyte precursors as particles having a size of fifty microns or less (<50pm), preferably ten microns or less ( <10pm), more preferably one micron or less (<1mih), and then initiating fixation of the organo-gel electrolytes on the surface or within the particles by non-contact energy input.

9. The method according to any one of the preceding claims, wherein the particles are cooled rapidly after heating at the surface to achieve an improvement in internal homogeneity, preferably by transferring the heated particles in a microwave-transparent liquid, which at room temperature (about 20 ° C) is present.

10. The method according to any one of the preceding claims, wherein the particles are heated in a suitable for the removal of alkali or alkaline earth metals atmosphere, preferably ammonia (NH ₃ ) and / or sulfur hexafluoride (SF _Ö ) by contactless energy input.

11. Process for coating bodies, preferably transition metal or metal particles, transition metal or metal oxide particles, transition metal or metal mixed oxide particles, or silicon or sulfur particles, more preferably those having a mass of less than one milligram and / or are present as grains, fibers, hollow fibers or 2D structures, by heating in the absence of oxygen with simultaneous presence of a carbon source.

12. The method of claim 11, wherein the energy input is contactless, preferably by electromagnetic radiation of a wavelength of 200nm to 50cm, more preferably by microwave radiation having a wavelength of 1 to 50 cm.

13. The method of claim 11 or 12, wherein the carbon source is liquid or gaseous, more preferably as a microwave-transparent compound, particularly preferably individually or in combination with each other: liquid: pentane, hexane, heptane, octane, nonane, decane, including all isomers For example, n-hexane, 2-methylpentane, and all cyclic forms, such as cyclohexane or gaseous: methane, ethane, propane, n-butane and iso-butane, with gases more preferably as part of an oxygen-free mixture with nitrogen and / or argon and / or hydrogen.

14. A material obtainable by the process according to the preceding claims, preferably doped with a transition metal having a larger atomic radius, preferably with yttrium, wherein preferably the proportion of the starting material is 90% or greater, and the proportion of the doping material is 10% or less.

15. Use of a material prepared according to any one of claims 1 to 13 in batteries and / or electrochemical systems.

16. A method for battery production, wherein the battery is present as an alkali-ion-free battery precursor cell array and the alkali ion is injected in liquid form into the individual chambers of the cells, preferably as a solution Salt of the alkali or alkaline earth metal in a suitable solvent, more preferably in water or dimethyl sulfoxide (DMSO).

17. The method of claim 16, wherein one or more of the following parameters are measured and optionally varied in a suitable form: stress,

Temperature, pressure, impedance, molarity / concentration and flow rate of the alkali-ion-containing liquid.